Alkyl Aromatic Hydroalkylation for the Production of Plasticizers

ABSTRACT

Provided are compounds of the following: 
     
       
         
         
             
             
         
       
     
     wherein R 1  is a saturated or unsaturated cyclic hydrocarbon optionally substituted with an alkyl and/or an OXO-ester, and R 2  is a C 4  to C 14  hydrocarbyl, preferably the residue of a C 4  to C 14  OXO-alcohol. Also provided are processes for making the compounds and plasticized polymer compositions containing said compounds.

PRIORITY

This application claims priority to and the benefit of U.S. applicationSer. No. 13/751,835, filed Jan. 28, 2013, the disclosure of which isincorporated herein by reference in its entirety. This application is acontinuation-in-part of U.S. application Ser. No. 13/751,835, filed Jan.28, 2013.

FIELD

This disclosure relates to a route to non-phthalate, aromatic esterplasticizers.

BACKGROUND

Plasticizers are incorporated into a resin (usually a plastic orelastomer) to increase the flexibility, workability, or distensibilityof the resin. The largest use of plasticizers is in the production of“plasticized” or flexible polyvinyl chloride (PVC) products. Typicaluses of plasticized PVC include films, sheets, tubing, coated fabrics,wire and cable insulation and jacketing, toys, flooring materials suchas vinyl sheet flooring or vinyl floor tiles, adhesives, sealants, inks,and medical products such as blood bags and tubing, and the like.

Other polymer systems that use small amounts of plasticizers includepolyvinyl butyral, acrylic polymers, nylon, polyolefins, polyurethanes,and certain fluoroplastics. Plasticizers can also be used with rubber(although often these materials fall under the definition of extendersfor rubber rather than plasticizers). A listing of the majorplasticizers and their compatibilities with different polymer systems isprovided in “Plasticizers,” A. D. Godwin, in Applied Polymer Science21st Century, edited by C. D. Craver and C. E. Carraher, Elsevier(2000); pp. 157-175.

Plasticizers can be characterized on the basis of their chemicalstructure. The most important chemical class of plasticizers is phthalicacid esters, which accounted for 85% worldwide of PVC plasticizer usagein 2002. However, in the recent past there has been an effort todecrease the use of phthalate esters as plasticizers in PVC,particularly in end uses where the product contacts food, such as bottlecap liners and sealants, medical and food films, or for medicalexamination gloves, blood bags, and IV delivery systems, flexibletubing, or for toys, and the like. For these and most other uses ofplasticized polymer systems, however, a successful substitute forphthalate esters has heretofore not been found.

One such suggested substitute for phthalates are esters based oncyclohexanoic acid. In the late 1990's and early 2000's, variouscompositions based on cyclohexanoate, cyclohexanedioates, andcyclohexanepolyoate esters were said to be useful for a range of goodsfrom semi-rigid to highly flexible materials. See, for instance, WO99/32427, WO 2004/046078, WO 2003/029339, WO 2004/046078, U.S.Application No. 2006-0247461, and U.S. Pat. No. 7,297,738.

Other suggested substitutes include esters based on benzoic acid (see,for instance, U.S. Pat. No. 6,740,254, and also co-pending,commonly-assigned, U.S. Provisional Patent Application No. 61/040,480,filed Mar. 28, 2008) or polyketones, such as described in U.S. Pat. No.6,777,514; and also co-pending, commonly-assigned, U.S. PatentPublication No. 2008/0242895, filed Mar. 28, 2008. Epoxidized soybeanoil, which has much longer alkyl groups (C₁₆ to C₁₈) has been tried as aplasticizer, but is generally used as a PVC stabilizer. Stabilizers areused in much lower concentrations than plasticizers. Copending andcommonly assigned U.S. Provisional Patent Application No. 61/203,626,filed Dec. 24, 2008, discloses triglycerides with a total carbon numberof the triester groups between 20 and 25, produced by esterification ofglycerol with a combination of acids derived from the hydroformylationand subsequent oxidation of C₃ to C₉ olefins, having excellentcompatibility with a wide variety of resins.

U.S. Pat. No. 2,520,084 to Dazzi discloses plasticized vinyl chloridepolymers using esters of phenyl benzoic acids and aliphatic hydrocarbonalcohols as plasticizers. Suitable esters are 2-ethylhexylm-phenylbenzoate, the corresponding para- and ortho-phenylbenzoates, ormixtures thereof, and the various phenylbenzoates of n-hexyl,2-methylheptyl, dodecyl, dimethylheptyl, 2-butoxyethyl, and isooctylalcohols, and other homologous straight and branched alcohols having 8to 14 atoms. The butoxyethyl and 2-ethylhexyl esters of phenylbenzoicacid are exemplified.

-   “Esters of diphenic acid and their plasticizing properties”, Kulev    et al., Izvestiya Tomskogo Politekhnicheskogo Instituta (1961) 111,    discloses diisoamyl diphenate, bis(2-ethylhexyl diphenate and mixed    heptyl, octyl and nonyl diphenates, prepared by esterification of    diphenic acid, useful as plasticizers for vinyl chloride.-   “Synthesis of dialkyl diphenates and their properties”, Shioda et    al., Yuki Gosei Kagaku Kvokaishi (1959), 17, discloses dialkyl    diphenates of C₁ to C₈ alcohols, useful as plasticizers for    poly(vinyl chloride) formed by converting diphenic acid to diphenic    anhydride and esterifying the diphenic anhydride, necessarily    resulting in 2,2′-substituted diesters of diphenic anhydride.

Other references of interest include: Clary, International Journal ofOrganic Chemistry, 2013, 3, 143-147; U.S. 2012/0108874 A1; and U.S. Pat.No. 5,138,022.

Thus, what is needed is a method of making a general purpose plasticizerhaving suitable melting or chemical and thermal stability, pour point,glass transition, increased compatibility, good performance and lowtemperature properties.

SUMMARY

In one aspect, the present application provides compounds of theformula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol.

In one aspect, the present application provides for mixtures comprisingtwo or more compounds of the formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol. In a preferred embodiment of the invention, the mixturecomprises two or more compounds of the formula above where the R₂ groupsare different. In a preferred embodiment of the invention, the mixturecomprises two or more compounds of the formula above where the R₂ groupsare the same.

In another aspect, the present application provides a process for makingcompounds of the formula:

wherein R₁ is a cyclic hydrocarbon optionally substituted with an alkyland/or an OXO-ester, and R₂ is a C₄ to C₁₄ hydrocarbyl, preferably ahydrocarbon residue of a C₄ to C₁₄ OXO-alcohol, comprising the steps of:reacting benzene or alkylated benzene under conditions appropriate toform alkylated biphenyl; optionally alkylating biphenyl to form saidalkylated biphenyl; oxidizing the alkyl group(s) on said alkylatedbiphenyl to form at least one acid group; and reacting said acidgroup(s) with an OXO-alcohol under esterification conditions to formsaid compounds.

In another aspect, the present application provides a polymercomposition comprising a thermoplastic polymer and at least oneplasticizer of the formula:

wherein R₁ is a saturated and unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of dynamic mechanical analysis of the plastisols ofExample 28.

FIG. 2 is a graphed elastic modulus plotted as a function of heatingtemperature for Example 29A.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Unless otherwise indicated, room temperature is about 21° C.

There is an increased interest in developing new plasticizers that offeralternatives to phthalates and which possess good plasticizerperformance characteristics but are still competitive economically. Thepresent disclosure is directed towards non-phthalate, mono- or diesterplasticizers, particularly OXO-ester plasticizers, that can be made fromlow cost feeds and employ fewer manufacturing steps in order to meeteconomic targets.

It has been determined that compounds of the general formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon, optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably the residue of a C₄ to C₁₄ OXO-alcohol, areparticularly useful as replacements for general purpose phthalateplasticizers like bis(2-ethylhexyl) phthalate (DEHP) ordi-isononylphthalate (DINP) or di-isodecyl phthalate (DIDP) ordi-2-propylheptyl phthalate (DPHP), which are the largest volumeplasticizers used in conventional polymer plastics. In any embodiment ofthe invention described herein, R₁ is an aromatic ring, preferably asubstituted aromatic ring, preferably a C₆ aromatic ring, preferably asubstituted C₆ aromatic ring, preferably an alkyl substituted C₆aromatic ring, preferably a methyl substituted C₆ aromatic ring.

In one aspect, the present application provides for mixtures comprisingtwo or more (alternately three, four, five, six, or more) compounds ofthe formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol. In a preferred embodiment of the invention the mixturecomprises one or more compounds where R₁ is saturated, and one or morecompounds where R₁ is unsaturated. Alternately, in another preferredembodiment of the invention, the mixture comprises: 1) one or morecompounds where R₁ is a saturated C₆ ring optionally substituted with analkyl and/or an OXO-ester, and 2) one or more compounds where R₁ is anunsaturated C₆ ring optionally substituted with an alkyl and/or anOXO-ester.

In any embodiment of the invention described herein R₁ may be located atthe ortho-, meta- or para-position. In any embodiment of the inventiondescribed herein R₁ may be phenyl located at the para-position. In anyembodiment of the invention described herein R₁ may be an alkyl and/oran OXO-ester-substituted phenyl at the ortho-, meta-, or para-position,preferably R₁ is an alkyl and/or an OXO-ester-substituted cyclohexyl atthe ortho-, meta-, or para-position, such as phenyl, methyl phenyl,benzyl, and the like. In any embodiment of the invention describedherein R₁ may be a substituted phenyl located at the ortho-, meta- orpara-position. In any embodiment of the invention described herein R₁may be phenyl located at the para-position, preferably a substitutedphenyl. In any embodiment of the invention described herein R₁ may bephenyl located at the para-position, preferably a substituted phenyl,where the phenyl is substituted with a C₁ to C₂₀ alkyl, preferably a C₁to C₄ alkyl, preferably a C₁ alkyl at the ortho-, meta- orpara-position, for example R¹ may be tolyl. The phenyl group may besubstituted at the 1, 2, 3, 4 or 5 positions, preferably at one positionwith a C₁ to C₂₀ alkyl, such as methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomersthereof.

In any embodiment of the invention described herein, R₂ may be a C₄ toC₁₄ hydrocarbyl, preferably a C₅ to C₁₄ hydrocarbyl, such as butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl and an isomer thereof, preferably C₅, C₆, C₉ and C₁₀hydrocarbyl, preferably a C₅ to C₁₁, preferably C₆ to C₁₀ hydrocarbyl.

In another embodiment of the invention, R₁ is substituted with an

group, where R₃ is a C₄ to C₁₄ hydrocarbyl, preferably a hydrocarbonresidue of a C₄ to C₁₄ OXO-alcohol, preferably a C₅ to C₁₀ hydrocarbyl,such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl or an isomer thereof, preferably a C₅, C₆,C₉ or C₁₀ hydrocarbyl. In any embodiment of the invention, R₁ may be thesame as the

group of the general formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon, optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably the residue of a C₄ to C₁₄ OXO-alcohol.

In any embodiment of the invention described herein R₂ may be thehydrocarbon residue of a C₅ to C₁₀ OXO-alcohol averaging from 0.2 to 5.0branches per residue.

In any embodiment of the invention described herein the hydrocarbonresidue averages from 0.05 to 0.4 branches per residue at the alcoholicbeta carbon.

In any embodiment of the invention described herein the hydrocarbonresidue averages at least 1.3 to 5.0 methyl branches per residue.

In any embodiment of the invention described herein the hydrocarbonresidue averages from 0.35 to 1.5 pendant methyl branches per residue.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula:

where each R₂ is, independently, a C₄ to C₁₄ hydrocarbyl, preferably theresidue of a C₄ to C₁₄ OXO-alcohol, preferably each R₂ is,independently, a C₆ to C₉ hydrocarbyl, preferably a C₆, C₇, C₈ or C₉hydrocarbyl, preferably a C₆, C₇, C₈ or C₉ alkyl, such as hexyl, heptyl,octyl or nonyl, or an isomer thereof.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula:

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂ is C₉H₁₉, C₁₀H₂₁ orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula:

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂ is C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein may be a mixture of the following at any ratio:

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂ is C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formulas:

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formulas:

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula (or comprise a mixture ofcompounds represented by the formulas):

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula (or comprise a mixture ofcompounds represented by the formulas):

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula (or comprise a mixture ofcompounds represented by the formulas):

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula (or comprise a mixture ofcompounds represented by the formulas):

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula (or comprise a mixture ofcompounds represented by the formulas):

wherein R²=a C₅ to C₁₄ hydrocarbyl, preferably R₂=C₉H₁₉, C₁₀H₂₁, orC₁₃H₂₇.

Additionally, compositions described by of the formulas depicted hereinmay be partially or fully hydrogenated, such that the final compositionmay contain compounds represented by the formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon, optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a C₄ to C₁₄hydrocarbyl, preferably the residue of a C₄ to C₁₄ OXO-alcohol, forexample:

wherein R₃ is an alkyl and/or an OXO-ester (such as methyl or —CO₂R₂*),R₂ is a C₄ to C₁₄ hydrocarbyl, preferably the residue of a C₄ to C₁₄OXO-alcohol, R₂* is a C₄ to C₁₄ hydrocarbyl, preferably the residue of aC₄ to C₁₄ OXO-alcohol, that may be the same or different as R₂.

In a preferred embodiment of the invention, the compound is representedby the formulas:

wherein each R₁ is, independently, a saturated or unsaturated cyclichydrocarbon, optionally substituted with an alkyl and/or an OXO-ester,and each R₂ is, independently, a C₄ to C₁₄ hydrocarbyl, preferably theresidue of a C₄ to C₁₄ OXO-alcohol, preferably the compound is a mixtureof compounds represented by the formulas:

and one or more of

wherein each R₃ is, independently, an alkyl and/or an OXO-ester (such asmethyl or —CO₂R₂*), R₂ is a C₄ to C₁₄ hydrocarbyl, preferably theresidue of a C₄ to C₁₄ OXO-alcohol, R₂* is a C₄ to C₁₄ hydrocarbyl,preferably the residue of a C₄ to C₁₄ OXO-alcohol, that may be the sameor different as R₂.

In a preferred embodiment of the invention in any formula describedherein, R¹ is tolyl and R² is a C₉ or C₁₀ hydrocarbyl.

In a preferred embodiment of the invention in any formula describedherein, R² is not linear, preferably R² is not a linear C₄ or C₅hydrocarbyl, preferably R² is not a linear group containing 4 or 5carbon atoms. In a preferred embodiment of the invention in any formuladescribed herein, R² is branched or cyclic, preferably branched.

In a preferred embodiment of the invention, the compounds producedherein may be a mixture of two, three, four or more compounds producedherein at any ratio. In an embodiment of the invention, the firstcompound is present at 0.1 to 99.8 wt % (preferably 1 to 98 wt %,preferably 5 to 94.9 wt %, preferably 10 to 89.9 wt %), the secondcompound is present at 0.1 to 99.8 wt % (preferably 1 to 98 wt %,preferably 5 to 94.9 wt %, preferably 10 to 89.9 wt %), and eachadditional compound is present at least 0.1 wt %, preferably at least 1wt %, preferably at least 5 wt %, preferably at least 10 wt %, basedupon the weight of the plasticizer compounds.

In a preferred embodiment of the invention, the compounds producedherein are represented by the formula:

where R is a linear C₆ or C₉ hydrocarbyl, is derived from a C₆ or C₉alcohol, or when R is the resulting structure from an OXO-alcohol,alternately R is linear and has 7, 8, 10, 11, 12 or 13 carbon atoms.

One route to non-phthalate plasticizers of the present disclosure is bycombination of two benzene molecules, by controlled hydrogenation, asfollows:

According to this method, the cyclohexyl benzene so formed can beoptionally dehydrogenated to form biphenyl as follows:

In either case, the aromatic ring(s) are subsequently alkylated with analcohol, such as methanol, which acts to add one or more methyl groupsto the ring(s), followed by oxygenation of the pendant methyl group(s)to form carboxylic acid group(s), and subsequently esterified with analcohol, ROH, to form the mono- or diesters of the present disclosureand subsequently hydrogenated with an hydrogen over hydrogenationcatalyst, to form one or more saturated ring:

wherein ROH is a branched alcohol, preferably an OXO-alcohol, even morepreferably a C₄ to C₁₄ OXO-alcohol.

Another route to non-phthalate plasticizers of the present disclosure isby oxidative coupling of two benzene molecules to form biphenyl, asfollows: For benzene coupling: Ukhopadhyay, Sudip; Rothenberg, Gadi;Gitis, Diana; Sasson, Yoel. Casali Institute of Applied Chemistry,Hebrew University of Jerusalem, Israel. Journal of Organic Chemistry(2000), 65(10), pp. 3107-3110. Publisher: American Chemical Society,incorporated herein by reference.

Similarly to the first process, the biphenyl molecule is then alkylated,for example, with an alcohol, such as methanol, to add one or moremethyl groups to the ring(s), followed by oxygenation of the pendantmethyl group(s) to form carboxylic acid group(s), and subsequentlyesterified with an alcohol, ROH, to form the mono- or diesters of thepresent disclosure and subsequently hydrogenated with an hydrogen overhydrogenation catalyst, to form one or more saturated ring.

Of course, a similar process can be followed utilizing an alkylaromatic, such as toluene as the starting material in place of benzene:

wherein ROH is a branched alcohol, preferably an OXO-alcohol, even morepreferably a C₄ to C₁₄ OXO-alcohol. Either monoesters or diesters can beformed, or both, depending on reaction conditions. Likewise, byappropriate control of the oxidation step so as to oxidize only one ofthe pendant methyl groups, monoester compounds of the following generalformula can be formed:

Alternatively, one mole of toluene can be hydrogenated to form methylcyclohexene, and then the methyl cyclohexene used to alkylate anothermole of toluene, followed by dehydrogenation to form dimethyl biphenyl.

In a more preferred embodiment, the resulting alkylated aromaticcompound is oxidized to acid/diacid then esterified with OXO-alcohols,which are mixed linear and branched alcohol isomers, the formation ofwhich is described in more detail below.

“OXO-alcohols” are isomeric mixtures of branched, organic alcohols.“OXO-esters” are compounds having at least one functional ester moietywithin its structure derived from esterification of a carboxylic acidportion or moiety of a compound with an OXO-alcohol.

OXO-alcohols can be prepared by hydroformylating olefins, followed byhydrogenation to form the alcohols. “Hydroformylating” or“hydroformylation” is the process of reacting a compound having at leastone carbon-carbon double bond (an olefin) in an atmosphere of carbonmonoxide and hydrogen over a cobalt or rhodium catalyst, which resultsin addition of at least one aldehyde moiety to the underlying compound.U.S. Pat. No. 6,482,972, which is incorporated herein by reference inits entirety, describes the hydroformylation (OXO) process. Theresulting OXO-alcohols consist of multiple isomers of a given chainlength due to the various isomeric olefins obtained in theoligomerization process, described below, in tandem with the multipleisomeric possibilities of the hydroformylation step.

Typically, the isomeric olefins are formed by light olefinoligomerization over heterogeneous acid catalysts, such as by propyleneand/or butene oligomerization over solid phosphoric acid or zeolitecatalysts. The light olefins are readily available from refineryprocessing operations. The reaction results in mixtures of longer-chain,branched olefins, which are subsequently formed into longer chain,branched alcohols, as described below and in U.S. Pat. No. 6,274,756,incorporated herein by reference in its entirety. Olefins forhydroformylation can also be prepared by dimerization of propylene orbutenes through commercial processes such as the IFP Dimersol™ processor the Huls (Evonik) Octol™ process.

Branched aldehydes are then produced by hydroformylation of the isomericolefins. The resulting branched aldehydes can then be recovered from thecrude hydroformylation product stream by fractionation to removeunreacted olefins. These branched aldehydes can then be hydrogenated toform alcohols (OXO-alcohols). Single carbon number alcohols can be usedin the esterification of the acids described above, or differing carbonnumbers can be used to optimize product cost and performancerequirements. The “OXO” technology provides cost advantaged alcohols.Other options are considered, such as hydroformylation of C₄-olefins toC₅-aldehydes, followed by hydrogenation to C₅-alcohols, or aldehydedimerization followed by hydrogenation to C₁₀ alcohols.

“Hydrogenating” or “hydrogenation” is addition of hydrogen (H₂) to adouble-bonded functional site of a molecule, such as in the present casethe addition of hydrogen to the aldehyde moieties of a di-aldehyde, toform the corresponding di-alcohol, and saturation of the double bonds inan aromatic ring. Conditions for hydrogenation of an aldehyde arewell-known in the art and include, but are not limited to temperaturesof 0-300° C., pressures of 1-500 atmospheres, and the presence ofhomogeneous or heterogeneous hydrogenation catalysts such as, but notlimited to Pt/C, Pt/Al₂O₃ or Pd/Al₂O₃ and Ni. Useful hydrogenationcatalysts include platinum, palladium, ruthenium, nickel, zinc, tin,cobalt, or a combination of these metals, with palladium beingparticularly advantageous.

Alternatively, the OXO-alcohols can be prepared by aldol condensation ofshorter-chain aldehydes to form longer chain aldehydes, as described inU.S. Pat. No. 6,274,756, followed by hydrogenation to form theOXO-alcohols.

“Esterifying” or “esterification” is reaction of a carboxylic acidmoiety, such as an anhydride, with an organic alcohol moiety to form anester linkage. Esterification conditions are well-known in the art andinclude, but are not limited to, temperatures of 0-300° C., and thepresence or absence of homogeneous or heterogeneous esterificationcatalysts such as Lewis or Brønsted acid catalysts.

In a preferred embodiment, this invention relates to a process formaking compounds of the formula:

wherein R₁ is a cyclic hydrocarbon optionally substituted with an alkyland/or an OXO-ester, and R₂ is a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol, comprising the steps of: reacting benzene or alkylatedbenzene under conditions appropriate to form alkylated biphenyl;optionally alkylating biphenyl to form said alkylated biphenyl;oxidizing the alkyl group(s) on said alkylated biphenyl to form at leastone acid group; and reacting said acid group(s) with an OXO-alcoholunder esterification conditions to form said compounds.

In a preferred embodiment of the invention, the reacting step isconducted with benzene, and said optional alkylating step is conductedwith an alcohol (such as methanol).

In a preferred embodiment of the invention, the alkylating step isconducted in the presence of an acid catalyst.

In a preferred embodiment of the invention, the reacting step isconducted with benzene, further comprising the steps of: hydroalkylatingbenzene by reacting benzene in the presence of H₂ to hydrogenate onemole of said benzene to form cyclohexene, alkylating benzene with saidcyclohexene to form cyclohexylbenzene; dehydrogenating saidcyclohexylbenzene to form biphenyl; and alkylating one or both aromaticmoieties of said biphenyl to form said alkylated biphenyl, wherepreferably the hydroalkylating step is conducted in the presence of ahydrogenation catalyst, the alkylating step is conducted with analkylation catalyst, and the dehydrogenating step is conducted with adehydrogenation catalyst.

In a preferred embodiment of the invention, the hydrogenation catalystis selected from the group consisting of platinum, palladium, ruthenium,nickel, zinc, tin, cobalt, or a combination of these metals, withpalladium being particularly advantageous; the alkylation catalyst isselected from the group consisting of Zeolite, mixed metal oxides andthe dehydrogenation catalyst is selected from the group consisting ofplatinum, pladium, Ru, Rh, nickel, zinc, tin, cobalt and combinationsthereof.

In a preferred embodiment of the invention, the reacting step isconducted with benzene in the presence of oxygen and an oxidativecoupling catalyst, forming biphenyl, further comprising the step of:alkylating one or both aromatic moieties of said biphenyl to form saidalkylated biphenyl, preferably the alkylating step is conducted with analkylation catalyst.

In a preferred embodiment of the invention, the reacting step isconducted with toluene, further comprising the steps of: reactingtoluene in the presence of H₂ and a hydrogenation catalyst to formmethyl cyclohexene; reacting said methyl cyclohexene with toluene in thepresence of an alkylation catalyst to form dimethyl cyclohexylbenzene;and dehydrogenating said dimethyl cyclohexylbenzene in the presence of adehydrogenation catalyst to form the alkylated biphenyl, which ispreferably dimethyl-biphenyl.

In a preferred embodiment of the invention, after reacting the acidgroup(s) with an OXO-alcohol under esterification conditions, thereaction product is contacted with a basic solution such as saturatedsodium bicarbonate or a caustic soda wash.

In a preferred embodiment of the invention, the crude ester is furtherstripped to remove excess alcohol and the stripped plasticizer istreated with activated carbon to improve the liquid volume resistivityof the plasticizer.

As discussed above, the resulting OXO-alcohols can be used individuallyor together in alcohol mixtures having different chain lengths, or inisomeric mixtures of the same carbon chain length to make mixed estersfor use as plasticizers. This mixing of carbon numbers and/or levels ofbranching can be advantageous to achieve the desired compatibility withPVC for the respective core alcohol or acid used for the polar moietyend of the plasticizer, and to meet other plasticizer performanceproperties. The preferred OXO-alcohols are those having from 5 to 13carbons, more preferably C₅ to C₁₁ alcohols, and even more preferably C₆to C₁₀ alcohols.

In one embodiment the preferred OXO-alcohols are those which have anaverage branching of from 0.2 to 5.0 branches per molecule, and from0.35 to 5.0 methyl branches per molecule, or even from 1.3 to 5.0 methylbranches per molecule. In a more preferred embodiment, the alcohols havefrom 0.05 to 0.4 branches per residue at the alcoholic beta carbon.

Typical branching characteristics of OXO-alcohols are provided in Table1, below.

TABLE 1 ¹³C NMR Branching Characteristics of Typical OXO-Alcohols. % ofβ- Total Pendant Pendant α- Branches Methyls Methyls Ethyls Avg. Carbonsper per per per OXO- Carbon w/ Mole- Mole- Mole- Mole- Alcohol No.Branches^(a) cule^(b) cule^(c) cule^(d) cule C₄ ^(e) 4.0 0 0.35 1.350.35 0 C₅ ^(f) 5.0 0 0.30 1.35 0.35 0 C₆ — — — — — — C₇ 7.2 0 0.13 2.2 —0.04 C₈ 8.0 0 0.08 2.6 — — C₉ 9.3 0 0.09 3.1 — — C₁₀ 10.1 0 0.08 3.1 — —C₁₂ 11.8 0 0.09 3.9 — — C₁₃ 12.7 0 0.09 3.9 — — — Data not available.^(a)—COH carbon. ^(b)Branches at the —CCH₂OH carbon. ^(c)This valuecounts all methyl groups, including C₁ branches, chain end methyls, andmethyl endgroups on C₂+ branches. ^(d)C₁ branches only. ^(e)Calculatedvalues based on an assumed molar isomeric distribution of 65% n-butanoland 35% isobutanol (2-methylpentanol). ^(f)Calculated values based on anassumed molar isomeric distribution of 65% n-pentanol, 30%2-methylbutanol, and 5% 3-methylbutanol.

In a preferred embodiment of the invention, the alcohol (such as anOXO-alcohol) has 2.0 to 3.5 methyl branches per molecule, typically 2.1to 3.3.

In general, for every polymer to be plasticized, a plasticizer isrequired with a good balance of polarity or solubility, volatility andviscosity to have acceptable plasticizer compatibility with the resin.In particular, if the 20° C. kinematic viscosity is higher than 250mm²/sec as measured by the appropriate ASTM test, or alternately if the20° C. cone-and-plate viscosity is higher than 250 cP, this will affectthe plasticizer processability during formulation, and can requireheating the plasticizer to ensure good transfer during storage andmixing of the polymer and the plasticizer. Volatility is also animportant factor which affects the ageing or durability of theplasticized polymer. Highly volatile plasticizers will diffuse andevaporate from the plastic resin matrix, thus losing mechanical strengthin applications requiring long term stability/flexibility. Relativeplasticizer loss from a resin matrix due to plasticizer volatility canbe roughly predicted by neat plasticizer weight loss at 220° C. usingThermogravimetric Analysis.

We have found that when C₄ to C₁₃ OXO-alcohols are used as reactants forthe esterification reactions described above, the resulting OXO-estersare in the form of relatively high-boiling liquids (having lowvolatility), which are readily incorporated into polymer formulations asplasticizers.

Any of the esters can have R₁ and R₂ which contain mixed alkyl isomerresidues of C₄ to C₁₃ OXO-alcohols, can be used as plasticizers forpolymers, such as vinyl chloride resins, polyesters, polyurethanes,silylated polymers, polysulfides, acrylics, ethylene-vinyl acetatecopolymer, rubbers, poly(meth)acrylics and combinations thereof,preferably polyvinylchloride.

In a preferred embodiment, this invention relates to polymer compositioncomprising a thermoplastic polymer and at least one plasticizerdescribed herein, such as a plasticizer of the formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a hydrocarbonresidue of a C₄ to C₁₄ OXO-alcohol, preferably where the thermoplasticpolymer is selected from the group consisting of vinyl chloride resins,polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers,poly(meth)acrylics and combinations thereof, alternately the polymer isselected from the group consisting of polyvinyl chloride (PVC),polyvinylidene chloride, a copolymer of polyvinyl chloride andpolyvinylidene chloride, and polyalkyl methacrylate (PAMA), preferablythe polymer is a copolymer of vinyl chloride with at least one monomerselected from the group consisting of vinylidene chloride, vinylacetate, vinyl propionate, vinyl butyrate, vinyl benzoate, methylacrylate, ethyl acrylate, and butyl acrylate.

In any embodiment of the invention, in the polymer compositioncomprising a thermoplastic polymer and at least one plasticizer, theamount of plasticizer is from 5 to 90 wt %, based upon the weight of thepolymer and plasticizer, preferably from 10 to 100 wt %, even morepreferably in the range from 15 to 90 wt %, preferably in the range from20 to 80 wt %.

The polymer composition comprising a thermoplastic polymer and at leastone plasticizer described herein may optionally contain furtheradditional plasticizers other than those produced herein, such as:dialkyl (ortho)phthalate, preferably having 4 to 13 carbon atoms in thealkyl chain; trialkyl trimellitates, preferably having 4 to 10 carbonatoms in the side chain; dialkyl adipates, having 4 to 13 carbon atoms;dialkyl sebacates preferably having 4 to 13 carbon atoms; dialkylazelates preferably having 4 to 13 carbon atoms; preferably dialkylterephthalates each preferably having 4 to 8 carbon atoms and moreparticularly 4 to 7 carbon atoms in the side chain; alkyl1,2-cyclohexanedicarboxylates, alkyl 1,3-cyclohexanedicarboxylates andalkyl 1,4-cyclohexanedicarboxylates, and preferably here alkyl1,2-cyclohexanedicarboxylates each preferably having 4 to 13 carbonatoms in the side chain; dibenzoic esters of glycols; alkylsulfonicesters of phenol with preferably one alkyl radical containing 8 to 22carbon atoms; polymeric plasticizers (based on polyester in particular),glyceryl esters, acetylated glycerol esters, epoxy estolide fatty acidalkyl esters, citric triesters having a free or carboxylated OH groupand for example alkyl radicals of 4 to 9 carbon atoms, alkylpyrrolidonederivatives having alkyl radicals of 4 to 18 carbon atoms and also alkylbenzoates, preferably having 7 to 13 carbon atoms in the alkyl chain. Inall instances, the alkyl radicals can be linear or branched and the sameor different.

The polymer composition comprising a thermoplastic polymer and at leastone plasticizer described herein prepared according to the presentinvention may further contain additives to optimize the chemical,mechanical or processing properties, said additives being moreparticularly selected from the group consisting of fillers, such ascalcium carbonate, titanium dioxide or silica, pigments, thermalstabilizers, antioxidants, UV stabilizers, lubricating or slip agents,flame retardants, antistatic agents, biocides, impact modifiers, blowingagents, (polymeric) processing aids, viscosity depressants or regulatorssuch as thickener and thinners, antifogging agents, optical brighteners,etc.

Thermal stabilizers useful herein include all customary polymerstabilizers, especially PVC stabilizers in solid or liquid form,examples are those based on Ca/Zn, Ba/Zn, Pb, Sn or on organic compounds(OBS), and also acid-binding phyllosilicates such as hydrotalcite. Themixtures to be used according to the present invention may have athermal stabilizer content of 0.5 to 10, preferably 0.8 to 5 and morepreferably 1.0 to 4 wt %, based upon the weight of the polymercomposition.

It is likewise possible to use costabilizers with plasticizing effect inthe polymer composition comprising a thermoplastic polymer and at leastone plasticizer as described herein, in particular epoxidized vegetableoils, such as epoxidized linseed oil or epoxidized soya oil.

Antioxidants are also useful in the polymer composition comprising athermoplastic polymer and at least one plasticizer described herein andcan include sterically hindered amines—known as HALS stabilizers,sterically hindered phenols, such as Topanol™ CA, phosphites, UVabsorbers, e.g. hydroxybenzophenones, hydroxyphenylbenzotriazoles and/oraromatic amines. Suitable antioxidants for use in the compositions ofthe present invention are also described for example in “Handbook ofVinyl Formulating” (editor: R. F. Grossman; J. Wiley & Sons; New Jersey(US) 2008). The level of antioxidants in the mixtures of the presentinvention is typically not more than 10 pph, preferably not more than 8pph, more preferably not more than 6 pph and even more preferablybetween 0.01 and 5 pph (pph=parts per hundred parts of polymer).

Organic and inorganic pigments can be also used in the polymercomposition comprising a thermoplastic polymer and at least oneplasticizer as described herein. The level of pigments in thecompositions to be used according to the present invention is typicallynot more than 10 pph, preferably in the range from 0.01 to 5 pph andmore preferably in the range from 0.1 to 3 pph. Examples of usefulinorganic pigments are TiO₂, CdS, CoO/Al₂O₃, Cr₂O₃. Examples of usefulorganic pigments are for example azo dyes, phthalocyanine pigments,dioxazine pigments and also aniline pigments.

The polymer composition comprising a thermoplastic polymer and at leastone plasticizer described herein may contain one or more filler,including mineral and/or synthetic and/or natural, organic and/orinorganic materials, for example, calcium oxide, magnesium oxide,calcium carbonate, barium sulphate, silicon dioxide, phyllosilicate,carbon black, bitumen, wood (e.g. pulverized, as pellets, micropellets,fibers, etc.), paper, natural and/or synthetic fibers, glass, etc.

The compositions described herein can be produced in various ways. Ingeneral, however, the composition is produced by intensively mixing allcomponents in a suitable mixing container at elevated temperatures. Theplastic pellet or powder (typically suspension PVC, microsuspension PVCor emulsion PVC) is typically mixed mechanically, i.e. for example influid mixers, turbomixers, trough mixers or belt screw mixers with theplasticizer and the other components at temperatures in the range from60° C. to 140° C., preferably in the range from 80° C. to 100° C. Thecomponents may be added simultaneously or, preferably, in succession(see also E. J. Wickson “Handbook of PVC Formulating”, John Wiley andSons, 1993, pp. 747 ff). The blend of PVC, plasticizer and otheradditive as described above (e.g. the PVC compound or the PVC paste) issubsequently sent to the appropriate thermoplastic moulding processesfor producing the finished or semi-finished article, optionally apelletizing step is interposed.

The blends (e.g. the PVC compound or the PVC paste) are particularlyuseful for production of garden hoses, pipes, and medical tubing, floorcoverings, flooring tiles, films, sheeting, roofing, or roofing webs,pool liners, building protection foils, upholstery, and cable sheathingand wire insulation, particularly wire and cable coating, coatedtextiles and wall coverings.

The plasticizers of the invention are useful across the range ofplasticized polyvinyl chloride materials. The plasticizers of theinvention are useful in the production of semi-rigid polyvinyl chloridecompositions which typically contain from 10 to 40 pph, preferably 15 to35 pph, more preferably 20 to 30 pph of plasticizer (pph=parts perhundred parts PVC); flexible polyvinyl chloride compositions whichtypically contain from 40 to 60 pph, preferably 44 to 56 pph, morepreferably from 48 to 52 pph plasticizer; and highly flexiblecompositions which typically contain from 70 to 110 pph, preferably 80to 100 pph, more preferably 90 to 100 pph of plasticizer.

One widespread use of polyvinyl chloride is as a plastisol. A plastisolis a fluid or a paste consisting of a mixture of polyvinyl chloride anda plasticizer optionally containing various additives, such as thosedescribed above. A plastisol is used to produce layers of polyvinylchloride which are then fused to produce coherent articles of flexiblepolyvinyl chloride. Plastisols are useful in the production of flooring,tents, tarpaulins, coated fabrics such as automobile upholstery, in carunderbody coatings, in mouldings and other consumer products. Plastisolsare also used in footwear, fabric coating, toys, flooring products andwallpaper. Plastisols typically contain 40 to 200 pph, more typically 50to 150 pph, more typically 70 to 120 pph, more typically 90 to 110 pphof plasticizer.

In a preferred embodiment of the invention, one or more (such as two orthree) plasticizers produced herein are combined with a polymer such asPVC to form a PVC compound (typically made from suspension PVC) or a PVCpaste (typically made from an emulsion PVC). A particularly useful PVCin the PVC compound or paste is one having a K value above 70.Particularly preferred PVC compounds or paste comprise: 20 to 100 pphplasticizer(s) and/or 0.5 to 15 pph stabilizer(s), and/or 1 to 30 pph,preferably 15 to 30 pph, filler(s), even more preferably the filler iscalcium carbonate and the stabilizer is a calcium/zinc stabilizer. Theabove combination is useful in wire and cable coatings, particularlyautomobile wire and cable coating and or building wire insulation.

In general, a particularly good (i.e. low) glass transition temperatureis achievable for the polymer compositions of the present invention byusing plasticizer which itself has a low glass transition temperatureand/or by using a high plasticizer content. Polymer compositions of thepresent invention may have glass transition temperatures in the rangefrom −70° C. to +10° C., preferably in the range from −60° C. to −5° C.,more preferably in the range from −50° C. to −20° C. and most preferablyin the range from −45° C. to −30° C. Tg of the polymer composition isdetermined using DMTA and DSC, as described below (In the event ofconflict between the DMTA and DSC results, DMTA shall be used). Tg ofthe neat plasticizer is determined using DSC as described below.

EXPERIMENTAL

The following examples are meant to illustrate the present disclosureand inventive processes, and provide where appropriate, a comparisonwith other methods, including the products produced thereby. Numerousmodifications and variations are possible and it is to be understoodthat within the scope of the appended claims, the disclosure can bepracticed otherwise than as specifically described herein.

EXAMPLES General Procedure for Esterification

Into a four necked 1000 ml round bottom flask equipped with an airstirrer, nitrogen inductor, thermometer, Dean-Stark trap and chilledwater cooled condenser were added an aromatic mono or (di)acid, and theOXO-alcohol(s). The Dean-Stark trap was filled with the OXO-alcohol(s).The reaction mixture was heated to 220° C. with air stirring under anitrogen sweep. The water that was produced was collected in theDean-Stark trap and was drained frequently. The theoretical weight ofwater was obtained in 3 hours at 220° C. indicating 96% conversion. Thereaction mixture was heated longer to achieve complete conversion to thediester. Excess alcohols plus some monoesters (in the case of diestersynthesis) were removed by distillation. The crude residual product wasoptionally treated with decolorizing charcoal with stirring at roomtemperature overnight. The mixture was then filtered twice to remove thecharcoal.

Example 1 Esterification of 4-Phenyl-Benzoic Acid with OXO-C₁₀ Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 4-phenyl-benzoic acid (101.8 g, 0.514 mole),OXO-C₁₀ alcohols (163 g, 1.027 mole), and OXO-C₁₀ alcohols (15.5 g,0.098 moles) were added to the Dean-Stark trap. The reaction mixture washeated for a total of 13 hours at 208-220° C. with gas chromatographic(GC) sampling. The product was then concentrated using a Claisenadapter, chilled water cooled condenser and receiving flask. The crudeproduct was a clear light yellow liquid, 99.5% purity by GC.

Example 2 Esterification of 4-Phenylbenzoic Acid with OXO-C₉ Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N2 inductor, Dean-Stark trap and chilled water cooledcondenser were added 4-phenylbenzoic acid (138 g, 0.6962 mole), OXO-C₉alcohols (201.1 g, 1.3924 mole) and xylenes (21.5 g, 0.202 mole). Thereaction mixture was heated for a total of 7 hours at 185-220° C. withGC sampling. The product was concentrated using a Claisen adapter,chilled water cooled condenser and receiving flask. The concentratedproduct was dissolved in an equal weight of toluene (180 g) and waswashed twice with 100 g of a 3 wt % sodium hydroxide solution followedby distilled water (100 g). The upper toluene phase was then dried overmagnesium sulfate, filtered and the toluene removed on a rotaryevaporator. The concentrated product was a clear and colorless liquidwith a purity of 99.5% monoesters by GC.

Example 3 Esterification of 3-Phenyl-Benzoic Acid with OXO-C₁₀ Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added biphenyl-3-carboxylic acid (50.0 g, 0.2522 mole),OXO-C₁₀ alcohols (79.7 g, 0.5044 mole), and xylenes (75 g, 0.706 moles)were added to the Dean-Stark trap. The reaction mixture was heated for atotal of 19 hours at 156-192° C. The product was concentrated using aClaisen adapter, chilled water cooled condenser and receiving flask. Theconcentrated product was dissolved in an equal weight of toluene (77 g)and was washed three times with 25 g of a 3 wt % sodium hydroxidesolution followed by distilled water (25 g) twice. The upper toluenephase was then dried over magnesium sulfate, filtered and distilledoverhead. The boiling point of the pure product was 175-183°C./0.27-0.28 mm vacuum. The purity of the distilled product was 99.2% byGC.

Example 4 Esterification of 2-Phenyl-Benzoic Acid with OXO-C₉ Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added biphenyl-2-carboxylic acid (99.4 g, 0.502 mole),OXO-C₉ alcohols (144.4 g, 1.003 mole), and OXO-C₉ alcohols (20 g, 0.14moles) were added to the Dean-Stark trap. The reaction mixture washeated for a total of 7 hours at 205-208° C. with GC sampling. Theproduct was distilled using a Claisen adapter, chilled water cooledcondenser and receiving flask. Two of the heart cuts were combined anddissolved in an equal weight of toluene (121.7 g) and were washed twicewith 50 g of a 3 wt % sodium hydroxide solution followed by distilledwater (50 g). The upper toluene phase was then dried over magnesiumsulfate, filtered then treated with decolorizing charcoal with stirringat room temperature for 2 hours. The product was filtered twice toremove all the charcoal. The toluene was then removed on the rotaryevaporator. The clear and colorless product was isolated and had apurity of 99.5% (by GC) monoesters.

Example 5 Blend of Example 1, 3 and 4

The following blend of pure monoesters was prepared: the ortho ester orbiphenyl-2-carboxylic acid plus OXO-C₉ alcohols (7.5 grams or 25 wt %),the meta ester biphenyl-3-carboxylic acid plus OXO-C₁₀ alcohols (15.0grams or 50 wt %) and the para monoester or biphenyl-4-carboxylic acidplus OXO-C₁₀ alcohols (7.5 grams or 25 wt %).

Example 6 Esterification of 4-Cyclohexyl Benzoic Acid with OXO-C₁₀Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 4-cyclohexyl benzoic acid (100.64 g, 0.493 mole),OXO-C₁₀ alcohols (156.5 g, 0.986 mole), and OXO-C₁₀ alcohols (15.5 g,0.098 moles) were added to the Dean-Stark trap. The reaction mixture washeated for a total of 10 hours at 217-220° C. with GC sampling. Theproduct was then concentrated using a Claisen adapter, chilled watercooled condenser and receiving flask. The crude product was a clear &colorless liquid, 99.2% purity (by GC).

Example 7 Blend of Example 1 and 6

The following four blends (by weight) were prepared containing themonoester of 4-phenylbenzoic acid plus OXO-C₁₀ alcohols (example 1) andthe monoester of 4-cyclohexylbenzoic acid plus OXO-C₁₀ alcohols (example6):

7a: blend of example 1 (70%) plus example 6 (30%),

7b: blend of example 1 (70%) plus example 6 (30%),

7c: blend of example 1 (50%) plus example 6 (50%),

7d: blend of example 1 (30%) plus example 6 (70%).

Example 8 Esterification of 4′-Methylbiphenyl-4-Carboxylic Acid withOXO-C₉ Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 4-methylbiphenyl-4-carboxylic acid (100 g, 0.47114mole), OXO-C₉ alcohols (136.1 g, 0.9423 mole) and toluene (50 g, 0.54mole). The reaction mixture was heated for a total of 6 hours at187-221° C. with GC sampling. The product was then distilled using aClaisen adapter, chilled water cooled condenser and receiving flask. Theproduct distilled at 184-185° C./0.10 mm and was a clear, essentiallycolorless liquid with 99.6% purity (by GC).

Example 9 Esterification of 4′-Methylbiphenyl-2-Carboxylic Acid withOXO-C₉ Alcohols

Into a 4-necked 1000 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 2-(p-tolyl)benzoic acid (191.9 g, 0.9042 mole),OXO-C₉ alcohols (261.12 g, 1.8087 mole) and xylenes (19.4 g, 0.18 mole).The reaction mixture was heated for a total of 22 hours at 207-214° C.with GC sampling. The product was then distilled using a Claisenadapter, chilled water cooled condenser and receiving flask. The productdistilled at 145-162° C./0.10 mm and was a clear, essentially colorlessliquid of 99.86% purity (by GC).

Example 10 Esterification of 2′-Methyl-3-Biphenylcarboxylic Acid withOXO-C₁₀ Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 2′-methyl-3-biphenylcarboxylic acid (51 g, 0.24mole), OXO-C₁₀ alcohols (76 g, 0.481 mole) and xylenes (34.3 g, 0.323mole). The reaction mixture was heated for a total of 15 hours at145-182° C. with GC sampling. The product was concentrated using aClaisen adapter, chilled water cooled condenser and receiving flask. Theconcentrated product was dissolved in an equal weight of toluene (63.1g) and was washed twice with 30 g of a 3 wt % sodium hydroxide solutionfollowed by distilled water (30 g). The upper toluene phase was thendried over magnesium sulfate, filtered and distilled. The monoesterdistilled at Bp=175-182° C./0.10 mm. A clear off white liquid wasobtained with a purity of 99.42% (by GC).

Example 11 Preparation of 4′-Methyl-3-Biphenylcarboxylic Acid withOXO-C₁₀ Alcohols

Decyl 3-bromobenzoate was prepared from the condensation of3-bromobenzoic acid and OXO-C₁₀ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate). The ester was purified bydistillation: ¹H NMR (400 MHz, CDCl₃) δ 0.87-1.77 (m, 21H), 4.32 (m,2H), 7.32 (m, 1H), 7.67 (m, 1H), 7.98 (m, 1H), 8.18 (s, 1H). In a 3-neckflask, decyl 3-bromobenzoate (1 equiv) and p-tolylboronic acid (1.2equiv) were dissolved in toluene to make a 0.2 M solution with respectto the bromobenzoic ester and the mixture degassed with N₂. A 2 M,degassed solution of sodium carbonate (2.5 equiv) in H₂O:MeOH (4:1) wasadded. Palladium tetrakistriphenylphosphine (0.01 equiv) was added andthe mixture refluxed until completion. The reaction was cooled and thelayers separated. The aqueous layer was extracted with ethyl acetate andcombined organic layers were washed with brine, dried over MgSO₄,filtered and concentrated under reduced pressure. Purification of theresulting crude oil was achieved by vacuum distillation ¹H NMR (400 MHz,CDCl₃) δ 0.80-1.87 (m, 20H), 2.45 (s, 3H), 4.39 (m, 2H), 7.31 (d, J=8.0Hz, 2H), 7.56 (m, 3H), 7.80 (m, 1H), 8.05 (m, 1H), 8.32 (s, 1H).

Example 12 Preparation of 2′-Methyl-4-Biphenylcarboxylic Acid withOXO-C₁₀ Alcohols

Decyl 4-bromobenzoate was prepared from the condensation of4-bromobenzoic acid and OXO-C₁₀ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate) then purified by distillation. Decyl2-bromobenzoate was coupled with o-tolylboronic acid as described inExample 11. Spectral data is as follows: decyl2′-methylbiphenyl-4-carboxylate: ¹H NMR (400 MHz, CDCl₃) 0.85-1.91 (m,19H), 2.33 (s, 3H), 4.43 (m, 2H), 7.30 (m, 4H), 7.44 (d, J=8.0 Hz, 2H),8.15 (m, 2H).

Example 13 Preparation of 3′-Methyl-4-Biphenylcarboxylic Acid withOXO-C₁₀ Alcohols

Decyl 4-bromobenzoate was prepared from the condensation of4-bromobenzoic acid and OXO-C₁₀ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate): ¹H NMR (400 MHz, CDCl₃) δ 0.86-1.76(m, 20H), 4.30 (m, 2H), 7.57 (d, J=8.0 Hz, 2H), 7.90 (dd, J=2.2, 8.6 Hz,2H). Decyl 4-bromobenzoate was coupled with m-tolylboronic acid asdescribed in Example 11: ¹H NMR (400 MHz, CDCl₃) δ 0.88-1.80 (m, 19H),2.44 (s, 3H), 4.33 (m, 2H), 7.22 (d, J=8.0 Hz, 1H), 7.36 (m, 1H), 7.45(m, 1H), 7.66 (d, J=8.0 Hz, 2H), 8.11 (m, 2H); ¹³C NMR (100 MHz, CDCl₃)10.9-39.4 (9C), 21.7, 65.3, 124.5-130.2 (8C), 138.7 (2C), 140.2, 145.8,166.8.

Example 14 Preparation of 3′-Methyl-4-Biphenylcarboxylic Acid withOXO-C₉ Alcohols

Nonyl 4-bromobenzoate was prepared from the condensation of4-bromobenzoic acid and OXO-C₉ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate): ¹H NMR (400 MHz, CDCl₃) δ 0.87-1.78(m, 19H), 4.31 (m, 2H), 7.57 (d, J=8.4 Hz, 2H), 7.90 (dd, J=2.9, 9.4 Hz,2H). Nonyl 4-bromobenzoate was coupled with m-tolylboronic acid asdescribed in Example 11: ¹H NMR (400 MHz, CDCl₃) δ 0.90-1.78 (m, 19H),2.45 (s, 3H), 4.38 (m, 2H), 7.22 (d, J=8.4 Hz, 1H), 7.36 (m, 1H), 7.45(m, 2H), 7.66 (d, J=8.0 Hz, 2H), 8.11 (m, 2H); ¹³C NMR (100 MHz, CDCl₃)10.9-39.4 (8C), 21.7, 65.6, 124.5-130.2 (8C), 138.7 (2C), 140.2, 145.8,166.8.

Example 15 Preparation of 3′-Methyl-2-Biphenylcarboxylic Acid withOXO-C₁₀ Alcohols

Decyl 2-bromobenzoate was prepared from the condensation of2-bromobenzoic acid and OXO-C₁₀ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate): ¹H NMR (400 MHz, CDCl₃) δ 0.86-1.78(m, 23H), 4.33 (m, 2H), 7.35 (m, 2H), 7.65 (m, 1H), 7.78 (d, J=8.0 Hz,1H). Decyl 2-bromobenzoate was coupled with m-tolylboronic acid asdescribed in Example 11: ¹H NMR (400 MHz, CDCl₃) δ 0.72-1.39 (m, 21H),2.42 (s, 3H), 4.07 (m, 2H), 7.18 (m, 3H), 7.30 (m, 1H), 7.41 (m, 2H),7.53 (m, 1H), 7.85 (d, J=8.0 Hz, 1H).

Example 16 Preparation of 3′-Methyl-3-Biphenylcarboxylic Acid withOXO-C₁₀ Alcohols

Decyl 3-bromobenzoate was coupled with m-tolylboronic acid as describedin Example 11: ¹H NMR (400 MHz, CDCl₃) δ 0.89-1.81 (m, 21H), 2.45 (s,3H), 4.37 (m, 2H), 7.22 (d, J=8.0 Hz, 1H), 7.37 (t, J=8.0 Hz, 1H), 7.45(d, J=8.0 Hz, 2H), 7.52 (t, J=8.0 Hz, 1 H), 7.79 (d, J=8.0 Hz, 1H), 8.03(d, J=8.0 Hz, 1H), 8.29 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) 11.6-3.4(20C), 21.7, 65.4, 124.4 (2C), 128.1, 128.4 (2C), 128.6 (2C), 128.9,129.0, 131.2, 131.6 (2C), 166.9.

Example 17 Preparation of Mixed Blend Monoesters of MethylbiphenylCarboxylic Acids+Oxo Alcohols

The following three monoesters were combined: 4-methylbiphenyl-4-oxoC₉ester (example 8) (17.62 g), 2-methyl-biphenyl-3-oxoC₁₀ ester (example10) (3.86 g), and 4-methylbiphenyl-2-oxoC₉ ester (example 9) (3.95 g).

Example 18 Esterification of 2,2′-Biphenyl Dicarboxylic Acid with C₅Alcohols (65/35, 1-Pentanol/2-Methyl-1-Butanol)

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 2,2′-biphenyl dicarboxylic acid (100 g, 0.46 mole),and mixed C₅ alcohols (65/35, 1-pentanol/2-methyl-1-butanol) (165.0 g,1.875 mole) to approximate the component distribution of an OXO-C₅alcohol. The reaction mixture was heated for a total of 73 hours at137-169° C. with GC sampling. The product was concentrated using aClaisen adapter, chilled water cooled condenser and receiving flask. Theconcentrated product was dissolved in an equal weight of toluene (140 g)and was washed twice with 50 g of a 3 wt % sodium hydroxide solutionfollowed by distilled water (50 g). The upper toluene phase was thendried over magnesium sulfate, filtered and distilled. The diesterdistilled at Bp=174-184° C./0.10 mm. The purity obtained by GC analysiswas 99.1%. The distillate was clear yellow liquid and was treated withdecolorizing charcoal with stirring at room temperature for 2 hours. Theproduct was filtered twice to remove all the charcoal. Clear andcolorless sample was obtained.

Example 19 Esterification of 2,2′-Biphenyl Dicarboxylic Acid with C₆Alcohols (65/35, 1-Hexanol/2-Methyl-1-Pentanol)

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 2,2′-biphenyl dicarboxylic acid (199.3 g, 0.823mole), and C₆ alcohols (65/35, 1-hexanol/2-methyl-1-pentanol) (336.2 g,3.2903 mole) to approximate the component distribution of an OXO-C₆alcohol. The reaction mixture was heated a total of 24 hours at 150-155°C. with GC sampling. The product was concentrated using a Claisenadapter, chilled water cooled condenser and receiving flask. Theconcentrated product was dissolved in an equal weight of toluene (347 g)and was washed twice with 100 g of a 3 wt % sodium hydroxide solutionfollowed by distilled water (100 g). The upper toluene phase was thendried over magnesium sulfate, filtered and distilled. The diesterdistilled at Bp=189-191° C./0.10 mm. The distillates were clear yellowliquids and were dissolved in toluene then treated with decolorizingcharcoal with stirring at room temperature for 2 hours. The product wasfiltered twice to remove all the charcoal then distilled overhead. Aclear off white liquid was obtained Bp=184° C./0.10 mm with a purity of97.9% (by GC).

Example 20 Esterification of 2,2′-Biphenyl Dicarboxylic Acid with OXO-C₉Alcohols

Into a 4-necked 500 ml round bottom flask equipped with an air stirrer,thermometer, N₂ inductor, Dean-Stark trap and chilled water cooledcondenser were added 2,2′-biphenyl dicarboxylic acid (54.4 g, 0.252mole), and OXO-C₉ alcohols (145.4 g, 1.01 mole) and xylenes (50 g, 0.47mole). The reaction mixture was heated a total of 24 hours at 172-189°C. with GC sampling. The product was concentrated using a Claisenadapter, chilled water cooled condenser and receiving flask. Theconcentrated product was dissolved in an equal weight of toluene (99.7g) and was washed three times with 50 g of a 3 wt % sodium hydroxidesolution followed by distilled water (50 g) twice. The upper toluenephase was then dried over magnesium sulfate, filtered and distilled. Thediester distilled at Bp=237° C./0.25-0.30 mm. The distillates were clearyellow orange liquids and were distilled a second time at 206-215°C./0.22-0.16 mm vacuum. The distillate remained yellow so it wasdissolved in toluene then treated with decolorizing charcoal withstirring at room temperature for 2 hours. The product was filtered twiceto remove all the charcoal. A clear light yellow liquid was obtainedwith a purity of 99.4% by GC.

Example 21 Preparation of Dihexylbiphenyl 4,4′Dicarboxylate UsingLinear-C₆ Alcohols

Hexyl 4-bromobenzoate was prepared from the condensation of4-bromobenzoic acid and hexanol by refluxing in benzene with H₂SO₄ andwater removal via a Dean-Stark trap with subsequent wash with basicsolution (sodium bicarbonate). The ester was purified by distillation.

Under N₂, hexyl 4-bromobenzoate (1 equiv), bispinacolatodiboron (0.5equiv), potassium carbonate (3 equiv) and PdCl₂ dppf (0.02 equiv) weredissolved in DMSO to make a 0.15 M solution with respect to thebromobenzoic ester. The solution was degassed with N₂, then heated at80° C. overnight. Water and ethyl acetate were then added to the cooledreaction and the layers separated. The organic layer was extracted withethyl acetate, then the combined organic layers washed with 10% HCl,water and brine. It was then dried (MgSO₄), filtered and concentrated.The crude oil was purified by passage through a short silica gel column(eluting with 10:90 acetone:petroleum ether) and vacuum distillation.

Example 22 Preparation of Dihexyl Biphenyl-3,3′-Dicarboxylate UsingOXO-C₆ Alcohols

Hexyl 3-bromobenzoate was prepared from the condensation of3-bromobenzoic acid and OXO hexanol by refluxing in benzene with H₂SO₄and water removal via a Dean-Stark trap with subsequent wash with basicsolution (sodium bicarbonate). The ester was purified by distillation:¹H NMR (400 MHz, CDCl₃) δ 0.90 (m, 3H), 1.34 (m, 6H), 1.76 (m, 2H), 4.31(t, J=6.6 Hz, 2H), 7.30 (t, J=8.0 Hz, 1H), 7.65 (m, 1H), 7.95 (m, 1H),8.16 (s, 1H); ¹³C NMR (100 MHz, CDCl₃) 14.1, 22.6, 25.8, 28.8, 31.6,65.7, 122.6, 128.2, 130.0, 132.6, 132.7, 135.9, 165.4. Under N₂, hexyl3-bromobenzoate (1 equiv), bispinacolatodiboron (0.5 equiv), potassiumcarbonate (3 equiv) and PdCl₂ dppf (0.02 equiv) were dissolved in DMSOto make a 0.15 M solution with respect to the bromobenzoic ester. Thesolution was degassed with N₂, then heated at 80° C. overnight. Waterand ethyl acetate were then added to the cooled reaction and the layersseparated. The organic layer was extracted with ethyl acetate, then thecombined organic layers washed with 10% HCl, water and brine. It wasthen dried (MgSO₄), filtered and concentrated. The crude oil waspurified by passage through a short silica gel column (eluting with10:90 acetone:petroleum ether) and vacuum distillation: ¹H NMR (400 MHz,CDCl₃) δ 0.91 (m, 6H), 1.36 (m, 12H), 1.80 (m, 4H), 4.36 (t, J=6.6 Hz,2H), 7.54 (m, 2H), 7.81 (m, 2H), 8.06 (d, J=8.0 Hz, 2H), 8.30 (s, 2H);¹³C NMR (100 MHz, CDCl₃) 14.2 (2C), 22.7 (2C), 25.9 (2C), 28.9 (2C),31.6 (2C), 65.5 (2C), 128.4-131 (8C), 140.6 (4C), 166.6 (2C).

Example 23 Preparation of Dihexyl Biphenyl-3,4′-Dicarboxylate UsingOXO-C₆ Alcohols

Hexyl 4-bromobenzoate was prepared from the condensation of4-bromobenzoic acid and OXO-C₆ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate), then purified by distillation: ¹HNMR (400 MHz, CDCl₃) δ 0.86-1.76 (m, 13H), 4.31 (m, 2H), 7.58 (d, J=8Hz, 2H), 7.91 (d, J=8.0 Hz, 2H). Hexyl 3-bromobenzoate was prepared fromthe condensation of 3-bromobenzoic acid and OXO-C₆ alcohols by refluxingin benzene with water removal via a Dean-Stark trap, then purified bydistillation: ¹H NMR (400 MHz, CDCl₃) δ 0.91-1.77 (m, 11H), 4.34 (m,2H), 7.31 (m, 2H), 7.64 (m, 1H), 7.77 (d, J=8.0 Hz, 1H). Hexyl4-bromobenzoate (1 equiv), bispinacolatodiboron (1.1 equiv) andpotassium acetate (3 equiv) were dissolved in DMF to make a 0.25 Msolution with respect to the bromobenzoic ester. The mixture wasdegassed with N₂ and palladium diacetate (0.02 equiv) was added. Thereaction was heated between 80-90° C. until completion (approx. 5 h),then cooled. Water was added and the mixture extracted 3 times withethyl acetate. The combined organic layers were washed twice with waterand twice with brine, then dried (MgSO₄), filtered and concentratedunder reduced pressure. The unpurified grayish yellow oil was thentransferred to a 3-neck flask and dissolved in toluene to make a 0.2 Msolution. An equivalent of a hexyl 3-bromobenzoate and a 2 M solution ofpotassium carbonate (5 equiv) was added and the mixture degassed.Palladium tetrakistriphenylphosphine (0.01 equiv) was added and thereaction heated at reflux overnight. After cooling, the aqueous layerwas extracted with ethyl acetate and combined organic layers washedtwice with water and twice with brine. It was then dried (MgSO₄),filtered and concentrated. The crude oil was purified by passage througha short silica gel column (eluting with 10:90 ethyl acetate:hexanes)followed by vacuum distillation: ¹H NMR (400 MHz, CDCl₃) δ 0.90-1.79 (m,25H), 4.32 (m, 2H), 7.52 (t, J=8.0 Hz, 1H), 7.67 (d, J=8.0 Hz, 2H), 7.77(m, 1H), 8.03 (m, 1H), 8.11 (m, 2H), 8.28 (s, 1H); ¹³C NMR (100 MHz,CDCl₃) 11.4-35.9 (10C), 63.69, 65.4, 127.2 (2C), 128.5, 129.2, 129.3,129.9, 130.3 (2C), 131.5, 131.6, 140.5, 144.6, 166.6 (2C).

Example 24 Preparation of 2,3′-Biphenyldicarboxylate Using OXO-C₆Alcohols

Hexyl 2-bromobenzoate was prepared from the condensation of2-bromobenzoic acid and OXO-C₆ alcohols by refluxing in benzene withH₂SO₄ and water removal via a Dean-Stark trap with subsequent wash withbasic solution (sodium bicarbonate), then purified by distillation: ¹HNMR (400 MHz, CDCl₃) δ 0.91-1.77 (m, 11H), 4.34 (m, 2H), 7.31 (m, 2H),7.64 (d, J=8.0 Hz, 1H), 7.77 (d, J=8.0 Hz, 1H). Hexyl 3-bromobenzoate (1equiv), bispinacolatodiboron (1.1 equiv) and potassium acetate (3 equiv)were dissolved in DMF to make a 0.25 M solution with respect to thebromobenzoic ester. The mixture was degassed with N₂ and palladiumdiacetate (0.02 equiv) was added. The reaction was heated between 80-90°C. until completion (approx. 5 h), then cooled. Water was added and themixture extracted 3 times with ethyl acetate. The combined organiclayers were washed twice with water and twice with brine, then dried(MgSO₄), filtered and concentrated under reduced pressure. Theunpurified grayish yellow oil was then transferred to a 3-neck flask anddissolved in toluene to make a 0.2 M solution. An equivalent of a hexyl2-bromobenzoate and a 2 M solution of potassium carbonate (5 equiv) wasadded and the mixture degassed. Palladium tetrakistriphenylphosphine(0.01 equiv) was added and the reaction heated at reflux overnight.After cooling, the aqueous layer was extracted with ethyl acetate andcombined organic layers washed twice with water and twice with brine. Itwas then dried (MgSO₄), filtered and concentrated. The crude oil waspurified by passage through a short silica gel column (eluting with10:90 ethyl acetate:hexanes) followed by vacuum distillation: ¹H NMR(400 MHz, CDCl₃) δ 0.81-1.77 (m, 25H), 4.04 (m, 2H), 4.33 (m, 2H), 7.46(m, 1H), 7.50 (m, 4H), 7.89 (m, 1H), 8.03 (m, 2H); ¹³C NMR (100 MHz,CDCl₃) 14.9-35.4 (10C), 63.7, 65.4, 127.8, 128.2, 128.5, 129.6, 130.3,130.7, 130.9, 131.2, 131.5, 133.0, 141.7, 142.1, 166.6, 168.6.

Table 2 summarizes the conditions for forming different esters.

TABLE 2 Temp Purity, % Example # Acid Alcohol (° C.) by GC  1 4-phenylbenzoic acid OXO-C₁₀ 208-220 99.5  2 4-phenyl benzoic acid OXO-C₉185-220 99.5  3 3-phenyl benzoic acid OXO-C₁₀ 175-183 99.2  4 2-phenylbenzoic acid OXO-C₉ 205-208 99.6  5 Blend of examples 1, 3 and 4  64-cyclohexylbenzoic acid OXO-C₁₀ 217-220 99.2  7a blend ofbiphenyl-4-carboxylic acid (70%) plus OXO-C₁₀ 145-182 99.424-cyclohexylbenzoic acid (30%), 2′- methylbiphenyl-3-carboxylic acid  7bblend of biphenyl-4-carboxylic acid (70%) plus OXO-C₁₀ 208-220 99.64-cyclohexylbenzoic acid (30%),  7c blend of biphenyl-4-carboxylic acid(50%) plus OXO-C₁₀ 208-220 99.6 4-cyclohexylbenzoic acid (50%),  7dblend of biphenyl-4-carboxylic acid (30%) plus OXO-C₁₀ 208-220 99.64-cyclohexylbenzoic acid (70%),  8 4′-methylbiphenyl-4-carboxylic acidOXO-C₉ 184-185 99.6  9 4′-methylbiphenyl-2-carboxylic acid OXO-C₉145-162 99.86 10 2′-methylbiphenyl-3-carboxylic acid OXO-C₁₀ 175-18299.42 11 4′-methylbiphenyl-3-carboxylic acid OXO-C₁₀ 122′-methyl-3-biphenylcarboxylic acid OXO-C₁₀ 133′-methyl-4-biphenylcarboxylic acid OXO-C₁₀ 143′-methyl-4-biphenylcarboxylic acid OXO-C₉ 153′-methyl-2-biphenylcarboxylic acid OXO-C₁₀ 163′-methyl-3-biphenylcarboxylic acid OXO-C₁₀ 17 blend of examples 8, 9,&10 OXO-C₉ + OXO-C₁₀ NA NA 18 biphenyl-2,2′-dicarboxylic acid C₅ (65/35)n- 174-184 99.1 pentanol/2- 19 biphenyl-2,2′-dicarboxylic acid C₆(65/35) n- 189-191 97.9 hexanol/2- methylpentanol 20biphenyl-2,2′-dicarboxylic acid OXO-C₉ 206-215 99.4 21biphenyl-4,4′-dicarboxylic acid Linear C₆ alcohol 22biphenyl-4,4′-dicarboxylic acid OXO-C₆ 23 biphenyl-3,4′-dicarboxylicacid OXO-C₆ 24 biphenyl-2,3′-dicarboxylic acid OXO-C₆

The structures of the samples listed in the above table are shown below:

Method for Preparation of Plasticized Polymer Testing Bars by SolventMethod A:

A 5.85 g portion of the ester sample (or comparative commercialplasticizer DINP) was weighed into an Erlenmeyer flask which hadpreviously been rinsed with uninhibited tetrahydrofuran (THF) to removedust. A 0.82 g portion of a 70:30 by weight solid mixture of powderedDrapex™ 6.8 (Crompton Corp.) and Mark™ 4716 (Chemtura USA Corp.)stabilizers was added along with a stirbar. The solids were dissolved in117 mL uninhibited THF. Oxy Vinyls™ 240 F PVC (11.7 g) was added inpowdered form and the contents of the flask were stirred overnight atroom temperature until dissolution of the PVC was complete. The clearsolution was poured evenly into a flat aluminum paint can lid(previously rinsed with inhibitor-free THF to remove dust) of dimensions7.5″ diameter and 0.5″ depth. The lid was placed into an oven at 60° C.for 2 hours with a moderate nitrogen purge. The pan was removed from theoven and allowed to cool for a ˜5 min period. The resultant clear filmwas carefully peeled off of the aluminum, flipped over, and placed backevenly into the pan. The pan was then placed in a vacuum oven at 70° C.overnight to remove residual THF. The dry, flexible, typically almostcolorless film was carefully peeled away and exhibited no oiliness orinhomogeneity unless otherwise noted. The film was cut into small piecesto be used for preparation of test bars by compression molding (size ofpieces was similar to the hole dimensions of the mold plate). The filmpieces were stacked into the holes of a multi-hole steel mold plate,pre-heated to 170° C., having hole dimensions 20 mm×12.8 mm×1.8 mm (ASTMD1693-95 dimensions). The mold plate was pressed in a PHI companyQL-433-6-M2 model hydraulic press equipped with separate heating andcooling platforms. The upper and lower press plates were covered inTeflon™-coated aluminum foil and the following multistage pressprocedure was used at 170° C. with no release between stages: (1) 3minutes with 1-2 ton overpressure; (2) 1 minute at 10 tons; (3) 1 minuteat 20 tons; (4) 1 minute at 30 tons; (5) 3 additional minutes at 30tons; (6) release and 3 minutes in the cooling stage of the press (7°C.) at 30 tons. A knockout tool was then used to remove the sample barswith minimal flexion. Typically near-colorless, flexible bars wereobtained which, when stored at room temperature, showed no oiliness orexudation after pressing unless otherwise noted. The bars were allowedto age at room temperature for at least 1 week prior to evaluation ofphase behavior with Differential Scanning calorimetry (DSC) andthermo-physical properties with Dynamic Mechanical Thermal Analysis(DMTA).

Method for Preparation of Plasticized Polymer Testing Bars by MeltMixing Method B:

In a 250 ml beaker was added 2.7 g of an additive package containing a70/30 wt/wt of Paraplex G62 ESO/Mark 4716. To this was added 19.1 g ofplasticizer and the mixture was stirred with a spatula until blended.After blending, 38.2 g of PVC was added and the mixture was mixedforming a paste. The mixture was added to the melt mixture. A HaakeRheomix 600 mixer manufactured by Haake PolyLab System was preheated tothe desired mixing temperature (165° C. for most experiments). Acoarsely mixed sample consisting of plasticizer, polyvinylchloride andstabilizers was added to the mixer while stirring at 35 rpm. Afteraddition the mixer was stopped for one minute. The mixer was startedagain and the sample was mixed for five minutes. After mixing for fiveminutes the mixer was stopped and disassembled. The mixed sample wasremoved hot.

Bars were made using a Carver press according to the followingprocedure: The press was preheated with the mold at 170° C. The mold wasremoved hot and the plasticized PVC was placed on the mold. The mold wasput back into the press and remained there for 3 minutes withoutpressure. Then 10 tons of pressure was placed on the mold and remainedfor 1 minute, the pressure was increased to 15 tons and remained therefor another minute. Finally, the pressure was increased to 30 tons andremained at that pressure for 3 minutes. The pressure was released after3 minutes, then the mold was placed in the cold side of the press and 30tons of pressure was added for another 3 minutes. Most of the analyticaltesting was done one week after pressing.

98° C. Weight Loss Comparison of PVC Bars Plasticized with Esters VersusPVC Bars Plasticized with Commercial Plasticizer:

Two each of the PVC sample bars prepared above were placed separately inaluminum weighing pans and placed inside a convection oven at 98° C.Initial weight measurements of the hot bars and measurements taken atspecified time intervals were recorded and results were averaged betweenthe bars. The averaged results are shown in Table 5.

70° C. Humid Aging Clarity Comparison of PVC Bars Plasticized withEsters Versus PVC Bars Plasticized with Commercial Plasticizer:

Using a standard one-hole office paper hole punch, holes were punched intwo each of the sample bars prepared above ⅛″ from one end of the bar.The bars were hung in a glass pint jar (2 bars per jar) fitted with acopper insert providing a stand and hook. The jar was filled with ˜½″ ofdistilled water and the copper insert was adjusted so that the bottom ofeach bar was ˜1″ above the water level. The jar was sealed, placed in a70° C. convection oven, and further sealed by winding Teflon™ tapearound the edge of the lid. After 21 days the jars were removed from theoven, allowed to cool for ˜20 minutes, opened, and the removed bars wereallowed to sit under ambient conditions in aluminum pans (with the barspropped at an angle to allow air flow on both faces) or hanging from thecopper inserts for 14 days (until reversible humidity-induced opacityhad disappeared). The bars were evaluated visually for clarity. All barsexhibited complete opacity during the duration of the test and forseveral days after removal from the oven. Notes on 70° C. Humid AgingClarity and appearance properties of ester- and DINP-containing PVC barsare shown in Table 5A.

Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis(TGA) Property Study of Esters and Plasticized Bars:

Thermogravimetric Analysis (TGA) was conducted on the neat esters usinga TA Instruments TGA5000 instrument (25-450° C., 10° C./min, under 25 ccN₂/min flow through furnace and 10 cc N₂/min flow through balance;sample size approximately 10 mg). Table 4 provides comparisons ofvolatilities and glass transitions (Tg) of the different esterfractions. Tg's given in Table 4 are midpoints of the second heatsobtained by Differential Scanning calorimetry (DSC) using a TAInstruments Q2000 calorimeter fitted with a liquid N₂ cooling accessory.Samples were loaded at room temperature and cooled to −130° C. at 10°C./min and analyzed on heating to 75° C. at a rate of 10° C./min Table 5provides a volatility comparison of the neat and plasticized PVC bars.

TABLE 4 TGA TGA 5% TGA 10% TGA Wt 1% Wt Wt Loss Wt Loss Loss at DSCT_(g) Example Loss (° C.) (° C.) (° C.) 220° C. (%) (° C.)  1 182.5214.3 231.9 6.3 −64.7  2 177.3 207 221.9 9.2 −64.1  3 171.1 200.1 215.312.2 −66.7  4 150.5 179.8 194.5 28.1 −66.3  5 161.5 191.8 207.6 16.5−66.3  6 167.7 199.0 215.1 12.2 −75.2  7a 170.8 200.3 216.4 11.5 −68.0 7b 176.2 206.0 221.1 9.5 −69.2  7c 173.3 203.0 217.9 11.0 −71.3  7d172.5 201.6 216.3 11.8 −73.2  8 183.7 219.2 235.3 5.2 −80.6  9 173.9204.8 220.2 9.9 −73.6 10 171.8 203.7 219.9 10.1 −65.9 11 188.6 219.4235.3 5.1 −63.2 12 187.9 214.1 229.8 6.6 −63.9 13 192.1 222.9 238.7 4.4−65.9 14 185.3 216.4 232.1 5.9 −64.1 15 148.6 180.9 196.3 26.1 −67.7 16177.1 208.6 223.5 8.6 −66.9 17 173.1 208.2 224.6 8.2 −63.3 18 159.9188.6 203.1 19.8 −75.0 19 173.9 204.8 220.2 9.9 −73.6 20 166.1 192.8206.4 18.7 −76.0 21 — — — — — 22 — — — — — 23 216.06 249.13 265.1 1.195−64.0 24 — — — — — — Data not taken

TABLE 5 Plasticizer TGA TGA 5% TGA TGA % Used in 1% Wt Loss Wt Loss 10%Wt Wt Loss at Bar (° C.) (° C.) Loss (° C.) 220° C. None (Neat PVC)129.9 192.3 255.4 6.3  1 199.1 239.9 251.7 2.3  2 192.5 232.4 251.2 3.1 3 188.0 230.2 246.8 3.43  4 170.9 207.4 239.7 6.7  5 180.4 222.7 243.64.6  6 185.3 226.9 244.7 3.9  7a 191.1 233.0 246.0 3.1  7b 188.3 229.0244.7 3.6  7c 188.8 230.2 245.6 3.4  7d 186.5 226.8 244.2 3.9  8 206.1244.2 257.1 1.8  9 176.2 214.7 243.2 5.9 10 189.0 230.2 247.9 3.5 11194.7 235.9 248.2 2.7 12 187.3 229.5 245.1 3.5 13 196.5 238.7 249.3 2.414 192.1 235.1 246.7 2.7 15 169.0 210.2 235.2 6.7 16 191.5 234.8 246.12.9 17 191.2 237.6 252.1 2.8 18 184.3 225.2 249.2 4.2 19 188.5 231.9247.4 3.3 20 218.7 249.1 262.4 1.1 21 233.0 245.6 254.6 0.7 22 217.3250.9 265.5 1.1 23 229.6 251.7 265.0 0.8 24 202.3 243.9 253.3 1.8Demonstration of Plasticization of PVC with Different Esters Made Usingthis Disclosure Via Differential Scanning Calorimetry (DSC):

Differential Scanning calorimetry (DSC) was performed on thecompression-molded sample bars prepared above (PVC:plasticizerratio=2:1) using a TA Instruments Q2000 calorimeter fitted with a liquidN₂ cooling accessory. Samples were loaded at room temperature and cooledto −110° C. at 10° C./min, and then analyzed on heating at a rate of 10°C./min to 130-160° C. for plasticized PVC bars, and to 100° C. for thecomparative neat PVC bar. Small portions of the sample bars (typicalsample mass 5-7 mg) were cut for analysis, making only vertical cutsperpendicular to the largest surface of the bar to preserve the upperand lower compression molding “skins”. The pieces were then placed inthe DSC pans so that the upper and lower “skin” surfaces contacted thebottom and top of the pan. Table 6 provides the first heat Tg onset,midpoint, and end for neat PVC and the plasticized bars. A lowering andbroadening of the glass transition for neat PVC was observed uponaddition of the esters, indicating plasticization and extension of theflexible temperature range of use for neat PVC.

TABLE 5A Notes on 70° C. Humid Aging Clarity and Appearance of Ester-and DINP-Containing PVC Bars. Example No. (Ester Used in Bar) Notes onBar DINP⁽¹⁾ Flex and brownish  1 Similar to DINP  2 Very flex and clear 3 Very flex and colorless  4 Very flex and yellowish  5 Very flex andyellowish  6 Very flex and yellowish  7a More flex than DINP  7b Moreflex than DINP  7c Much more flex than DINP  7d Much more flex than DINP 8 NA  9 NA 10 Stiffer than DINP 11 NA 12 NA 13 NA 14 NA 15 Similar toDINP 16 A bit stiffer than DINP, similar color to DINP 17 Similar toDINP 18 Colorless and flex 19 Similar to DINP 20 Very stiff 21 NA 22More flex than DINP 23 Similar to DINP 24 Similar to DINP ⁽¹⁾Bars madefollowing example 44 method A ⁽²⁾Bars made following example 44 method B

TABLE 6 Plasticizer Used in T_(g) Onset T_(g) Midpt T_(g) End T_(m) Max(° C.) Bar (° C.) (° C.) (° C.) and DH_(f)(J/g)^(a) None 44.5 46.4 48.9not calc. (Neat PVC)  1 −35.3 −12.6 10.2 61.6, 1.4  2 −18.1 −1.1 16.155.3, 0.9  3 −39.5 −15.6 8.1 55.2, 1.1  4 −42.7 −18.9 4.9 60.1, 0.5  5−37.9 −13.8 10.4 55.2, 0.9  6 −39.0 −14.0 12.5 58.2, 0.9  7a −32.7 −10.611.5 54.1, 1.0  7b −30.4 −9.1 12.3 56.4, 1.1  7c −33.3 −10.6 12.4 56.3,1.0  7d −36.1 −13.4 10.0 55.5, 1.1  8 −17.2 −1.3 14.6 54.5, 0.3  9 −27.0−10.6 6.0 54.7, 86.1 and 0.5, 0.2, respectively 10 −39.4 −11.9 15.953.0, 1.1 11 −28.5 −8.0 12.7 52.3, 1.1 12 −65.5, −33.5 −61.3, −11.1−57.0, 11.7 55.2, 0.9 13 −25.5 −6.0 13.5 56.9, 0.9 14 −24.6 −4.6 15.456.0, 1.0 15 −36.6 −13.3 10.7 54.6, 0.8 16 −28.7 −8.7 11.6 54.5, 0.8 17−33.8 −13 8.3 55.1, 0.9 18 −15.9 −0.5 14.8 56.2, 0.8 19 −19.6 −3.6 12.456.7, 0.9 20 −18.5 −8.8 0.9 54.6, 1.1 21 −2.5 8.2 21.2 — 22 −31.0 10.210.6 53.5, 0.8 23 −19.2 −2.2 15.0 53.9, 0.8 24 −22.9 −8.2 6.9 58.2, 1.0— Data not obtained. ^(a)Most sample bars showed a weak melting point(T_(m)) from the crystalline portion of PVC. Often this weak transitionwas not specifically analyzed, but data is given here in instances whereit was recorded.Demonstration of Plasticization of PVC with Different Esters Via DynamicMechanical Thermal Analysis (DMTA):

A TA Instruments DMA Q800 fitted with a liquid N₂ cooling accessory anda three-point bend clamp assembly was used to measure thethermo-mechanical performance of neat PVC and the PVC/plasticizer blendsample bars prepared above. Samples were loaded at room temperature andcooled to −90° C. at a cooling rate of 3° C./min After equilibration, adynamic experiment was performed at one frequency using the followingconditions: 3° C./min heating rate, 1 Hz frequency, 20 μm amplitude,0.01 N pre-load force, force track 120%. Two or three bars of eachsample were typically analyzed and numerical data was averaged. The DMTAmeasurement gives storage modulus (elastic response modulus) and lossmodulus (viscous response modulus); the ratio of loss to storage moduliat a given temperature is tan δ (tan delta). The tan δ peak isassociated with the glass transition (temperature of the brittle-ductiletransition) and is more easily interpreted for plasticized systemscompared with the DSC curves. The beginning (onset) of the glasstransition, Tg, was obtained from the tan δ curve for each sample byextrapolating a tangent from the steep inflection of the curve and thefirst deviation of linearity from the baseline prior to the beginning ofthe peak. Table 7 provides a number of DMTA parameters for neat PVC andPVC bars plasticized with materials described above: Tg onset (takenfrom tan δ); peak of the tan δ curve; storage modulus at 25° C.; and thetemperature at which the storage modulus equals 100 MPa (thistemperature was chosen to provide an arbitrary measure of thetemperature at which the PVC loses a set amount of rigidity; too muchloss of rigidity may lead to processing complications for the PVCmaterial.). The storage modulus at 25° C. provides an indication ofplasticizer efficiency (i.e., the amount of plasticizer required toachieve a specific stiffness); the higher the storage modulus, the moreplasticizer required. The flexible use temperature range of theplasticized PVC samples is evaluated as the range between the Tg onsetand the temperature at which the storage modulus was 100 MPa. A loweringand broadening of the glass transition for PVC is observed upon additionof the esters, indicating plasticization and extension of the flexibletemperature range of use for PVC. Plasticization (enhanced flexibility)is also demonstrated by lowering of the PVC room temperature storagemodulus upon addition of the esters.

TABLE 7 Temp. Flexible Plasticizer Tan δ T_(g) Tan δ 25° C. Storage of100 MPa Use Used Onset Peak Mod. Storage Range in Bar (° C.) (° C.)(MPa) Mod. (° C.) (° C.)^(a) None (Neat 44.0 61.1 1433 57.1 13.1 PVC)  1−38.6 20.6 36.4 17.3 55.9  2 −28.3 19 35.7 17.1 45.4  3 −40.3 14.5 35.414.4 54.8  4 −34.8 20.2 48.5 19.1 53.9  5 −37.0 16.3 26.6 13.5 50.5  6−50.0 26.8 59.9 20.0 70.0  7a −34.7 23.1 35.0 16.9 51.5  7b −38.2 20.342.5 16.5 54.7  7c −42.7 19.5 58.2 18.2 60.9  7d −43.2 23.2 49.3 18.261.4  8 −20.5 23.4 52.4 20.5 41.0  9 −31.6 17.1 38.9 16.5 48.2 10 −45.223.1 49.1 18.4 63.6 11 −33.6 21.0 31.6 16.2 49.8 12 −40.9 27.1 66.3 21.462.4 13 −32.6 19.9 38.9 16.7 49.3 14 −27.0 20.4 38.4 16.8 43.8 15 −40.218.2 34.3 13.8 54.0 16 −38.0 17.8 34.6 14.7 52.6 17 −24.8 20.4 45.0 18.142.9 18 −26.7 21.0 37.5 17.5 44.2 19 −24.0 17.6 42.8 17.2 41.2 20 −28.124.5 61.3 20.6 48.7 21 18.2 47.1 1588 43.6 25.5 22 −24.9 20.7 37.4 16.741.6 23 −21.3 21.9 56.9 20.1 41.4 24 −27.4 18.9 35.8 12.0 39.4

Table 8 summarizes the useful tests for plasticizing performance usingesters from Examples 1-10; DINP (diisononylphthalate) is used forcomparison.

TABLE 8 Example No. (Ester Used Viscosity in Bar) (units) Tg Notes onfilms or bars DINP⁽¹⁾ 100 −79  1 134 −64.7 Flex and colorless similar toDINP  2 NA −64.1 Flex and colorless similar to DINP  3 133 −75.0 Flexand colorless similar to DINP  4 NA −66.3 Stiffer than DINP  5 NA −80.6Very flexible  6 104 −60.4 Flex, a bit darker than DINP  7a NA Similarto DINP  7b NA −75.1 Similar to DINP  7c NA −73.6 Similar to DINP  7d NASimilar to DINP  8 161.7 NA  9 NA NA 10 NA Similar to DINP 11 NA NA 12225.5 NA 13 204.1 NA 14 190.8 NA 15 105.5 Very dark and stiffer thanDINP 16 228.2 More flex than DINP 17 165.2 Similar to DINP 18 86.6Stiffer than DINP 19 117.8 Similar to DINP 20 259.5 Stiffer than DINPand exudates 21 NA NA 22 NA Very flex colorless 23 NA Similar to DINP 24NA More flex than DINP

Example 25

A PVC plastisol was prepared according the ASTM D1755 method, by mixingin a Hobart mixer 150 grams of the plasticizer of Example 1 the4-phenyl-benzoic acid isodecyl alcohol ester, 200 grams of PVC resin,and 6 grams of PVC stabilizer Mark 1221 (Ca/Zn stab) and at varyingspeeds for 10 minutes. The 1 hour plastisol viscosity after mixing was4410 cP measured at a shear rate of 180 l/s. By comparison a DINP(available from ExxonMobil Chemical) formulation prepared by the sameprocedure had a 1 hr plastisol viscosity of 2440 cp.

Weight losses after heating of this plastisol for 4 minutes at 200° C.were 0.21% versus 0.22% for a comparative example based on DINP and0.24% for a comparative example based on DOTP (available from Aldrich).Dynamic mechanical analysis of the plastisol as it was heated to finalfusion, gave an initial gelation temperature of 91° C., final gelationtemperature of 116° C., and a fusion temperature of 166° C. Thecomparative example based on DINP has a gelation temperature of 90° C.,a final gelation temperature of 128° C. and a fusion temperature of 173°C. Example 1, the 4-phenyl-benzoic acid isodecyl alcohol ester, wasfound to be faster fusing plasticizers with lower initial and finalgelation temperature.

Thin layers (10-15 mils) of the plastisol were fused in a Werner Mathysforced air oven for 3 minutes at 180° C., then combined and molded at170° C. for 15 minutes into test plaques. Evaluation of the molded testplaques gave a Shore A Hardness of 47, an ultimate tensile strength of2217 psi, a 100% modulus of 804 psi and an ultimate elongation of 406%.The comparative example based on DINP gave a Shore A Hardness of 49, anultimate tensile strength of 2211 psi, a 100% modulus of 777 psi and anultimate elongation of 416%. The comparative example based on DOTP gavea Shore A Hardness of 49, an ultimate tensile strength of 2209 psi, a100% modulus of 809 psi and an ultimate elongation of 411%. Shore AHardness was determined by ASTM D 2240-86. Tensile properties (includingultimate tensile strength, ultimate elongation) were determined by ASTMD 638 (30 mil test specimens, Type C die). Mechanical properties(including 100% modulus) were determined by ASTM D 638.

Example 26

The plasticizer from Example 1, the 4-phenyl-benzoic acid isodecylalcohol ester, was tested as plasticizer in flexible polyvinyl chlorideand compared to DINP available from ExxonMobil Chemical Company and DOTPavailable from Aldrich. All plasticizers were tested at the sameconcentrations. All formulations were prepared at the same plasticizerpph (parts per hundred parts of PVC) level. A solution was prepared bydissolving 0.5 grams of stearic acid with slight heating and stirring in120 grams of the plasticizer from Example 1. After the stearic aciddissolved, the solution was cooled to room temperature, and 6.0 grams ofthe PVC stabilizer Mark™ 1221 (Ferro) was added. This solution was thenadded to 200 grams of PVC resin (OXY™ 240F) and mixed under low speed ina Hobart mixer. The mixture was processed into a flexible PVC productthrough milling on a Dr. Collins roll mill, at 165° C. for 6 minutes.The milled sheet was removed from the roll mill, cooled to roomtemperature, and then portions of this product were pressed to testspecimens of various thicknesses, at 170° C. for 15 minutes. Aftercooling, the test specimens were removed from the molds, and conditionedfor 7 days at 22° C. and 50% relative humidity. The Shore A hardness(ASTM D 2240-86) and tensile properties (30 mil test specimens, Type Cdie) were measured and are reported in Table 26.

The mechanical properties (original) were obtained from samples in aZwick tensile tester (T1-FR005TN.A50) measuring the modulus at 100%extension, the ultimate tensile strength in psi and ultimate elongationin % according to ASTM D 638. The same mechanical properties weremeasured on dumbbells that had been aged at 100° C. for 7 days, 100° C.,with airflow of 150 air changes/hr. Retained tensile strength was 101%of the original tensile and elongation at break was 76% of the originalelongation at break.

The low temperature flexibility of the materials was measured using theClash and Berg test (ASTM D1043-84) gave a temperature of −15° C.

TABLE 26 Plasticizer from DINP DOTP Example 1 60 phr 60 phr 60 phr Oxy ™240 100 100 100 Mark ™ 1221 (Ca/Zn Stab.) 3.3 3.3 3.3 ESO (epoxidizedsoybean oil) 2.20 2.20 2.2 Stearic Acid 0.3 0.3 0.3 Original MechanicalProperties Shore A Hardness (15 sec.) 68 68 68 100% Modulus Strength,psi 1252 1304 1381 Ultimate Tensile Strength, psi 2695 2769 2927Ultimate Elongation, % 403 385 355 Retained Properties after ageing for10 days at 100° C. forced ventilation Retained 100% Modulus Strength, %132 135 170 Retained Tensile Strength, % 106 103 101 RetainedElongation, % 91 92 76 Carbon Volatility (24 hours at 70 C.) Mean (3specimens) 0.6 0.7 0.7 Low Temperature Clash Berg (Tf), ° C. −24 −32 −15

Example 27 Esterification of 4-Phenyl-Benzoic Acid

Into a five-necked, 2000 ml round bottom flask equipped with amechanical stirrer, nitrogen inductor, thermometer, Dean-Stark trap andchilled water cooled condenser were added 2 moles of 4-phenyl-benzoicacid (Acros™) and 2.5 moles of respectively Isodecyl alcohol (Exxal™10), of Isoundecyl alcohol (Exxal™ 11), of Isotridecyl alcohol (Exxal™13). The Dean-Stark trap was filled with alcohol. The alcohol was heatedat 100° C. under nitrogen and then degassed several times to removeremaining air. The acid was added in several steps (3) under vigorousstirring. The solution was heated until 180° C. and the catalyst (1%TIOT (toira-isooctyl titanates) on acid) mixed with 20 gr of alcohol wasslowly added. The vacuum was at 600 mm Hg. The addition of the catalystsolution took approx. 30 minutes. The temperature was progressivelyincreased to 210-215° C. and the vacuum was reduced to collect thewater. When, the theoretical amount of water was collected(approximately), the acid conversion was measured by titration. Thevacuum was further decreased (200 mm Hg) in order to collect the excessalcohol (for about one hour).

The mixture was cooled to 90° C. and a solution of Na₂CO₃ was added tohydrolyze and/or neutralize catalyst residues and/or neutralize anyresidual monoester. The ester was filtered via a suction filter withpaper filter and filter aid. Steam stripping was done at 160° C. bypassing steam (220° C.) through the ester to remove excess alcohol for1.5 hours at reduced pressure. The product was then dried with nitrogen(30 min) The ester was filtered at room temperature via a suction filterwith paper filter and filter aid (Perlite).

Neat properties of the three esters of example 27 are shown in the Tablebelow and are compared to DINP.

Solution temperature of plasticizers is defined as the temperature atwhich a set amount of PVC gets dissolved in a set amount of plasticizer.The solution temperature is not only influenced by the plasticizer typebut also by the PVC resin type and in particular the K Value (DIN 53408Testing of Plastics; Determination of Solubility Temperature ofPolyvinyl Chloride (PVC) in Plasticizers (1967.06.01)).

The solution temperature of the three plasticizers of example 27 werecompared with those of DINP and summarized in the table below. Esters ofthe invention made with C10 and C11 alcohols exhibit lower solution T°than DINP.

Neat plasticizers volatility at elevated temperatures in a forcedventilated oven were assessed (based on ASTM D 2288-97). 10 g neatplasticizer sample was poured into a cup (internal diameter 50 mm,thickness 0.18±0.02 mm and 35 mm height) and placed for 24 hours at 155°C. in a forced ventilated oven (Heraeus oven type UT 6050 UL over 160air renewal per hour). After 24 hours, the cups were cooled down in adesiccator and the plasticizer loss by evaporation was weighed.

Results are listed in the table below and indicate that all4-phenyl-benzoic acid esters of example 27 exhibit lower neat volatilitythan the comparative example DINP.

TABLE 27 Esters 4-phenyl- 4-phenyl- 4-phenyl- benzoic acid benzoic acidbenzoic acid DINP ester ester ester Alcohols Exxal ™ 10 Exxal ™ 11Exxal ™ 13 Viscosity (mPas) - 96 127.9 158.7 262.1 ASTM D445 Density(g/cm³) - 0.972 1.007 1.001 0.990 ASTM D4052 Solution 127 120 124 135temperature (in ° C.) Neat plasticizer 7.3 5.9 5 3.8 volatility at 155°C.- 24 h - forced ventilation (in wt %)

Example 28

PVC plastisols were prepared by mixing in a Hobart mixer. The plastisolswere prepared with 100 parts PVC (Solvin 382 NG), 60 parts of esteraccording to example 27, and 1 part of a conventional stabilizer. Thegelation temperatures of the plastisols were determined by an Anton PaarPhysica Rheometer MCR 301. The instrument was used in oscillation mode,frequency 1 hz, amplitude 0.01% and the heating rate was 10° C./minDynamic mechanical analysis of the plastisols as they were heated tofinal fusion, gave an initial gelation temperature of 103° C. (G′(Elastic modulus) is equal to 10⁵ Pa) for the 4-phenyl-benzoic acidisodecyl alcohol ester, an initial gelation temperature of 116° C. forthe 4-phenyl-benzoic acid isoundecyl alcohol ester and an initialgelation temperature of 136° C. for the 4-phenyl-benzoic acidisotridecyl alcohol ester. The comparative example, based on DINP had aninitial gelation temperature of 133° C. The 4-phenyl-benzoic acidisodecyl and isoundecyl alcohol esters were found to exhibit lowergelation T° and were faster fusing than DINP as shown on the DMA graph(FIG. 1). Note that in FIG. 1, elastic modulus is plotted as a functionof the heating temperature (heating rate is 10° C./min) The top line isthe plasticizer derived from the C₁₀ alcohol, the second to the top lineis the plasticizer derived from the C₁₁ alcohol, the third to the topline is DINP, and the bottom line is the plasticizer derived from theC₁₃ alcohol.

Example 29 Esterification of 4,4′-Biphenyl Dicarboxylic Acid with OXO-C₉Alcohol

Into a five-necked, 2000 ml round bottom flask equipped with amechanical stirrer, nitrogen inductor, thermometer, Dean-Stark trap andchilled water cooled condenser were added 1.2 moles of 4,4′biphenyldicarboxylic acid (Apollo) and 4.8 moles of Isononyl alcohol (Exxal™ 9).The Dean-Stark trap was filled with alcohol. The alcohol was heated at100° C. under nitrogen and then degassed several times to removeremaining air. The acid was added in several steps (3) under vigorousstirring. The solution was heated until 180° C. and the catalyst (1%TIOT on acid) mixed with 20 gr of alcohol was slowly added. The vacuumwas at 600 mm Hg. The addition of the catalyst solution took approx. 30minutes. The temperature was progressively increased to 210-220° C. andthe vacuum was reduced to collect the water. When the theoretical amountof water was collected, the acid conversion was measured by titration.

The vacuum was further decreased (200 mm Hg) in order to collect excessalcohol (for about one hour). The mixture was cooled to 90° C. and asolution of Na₂CO₃ was added to hydrolyze and/or neutralize catalystresidues and/or neutralize any residual monoester. The ester wasfiltered via a suction filter with paper filter and filter aid. Steamstripping was done at 160° C. by passing steam (220° C.) through theester to remove excess alcohol during for 1.5 hours at reduced pressure.The product was then dried with nitrogen (30 min). The ester wasfiltered at room temperature via a suction filter with paper filter andfilter aid (Perlite).

Example 29A

PVC plastisols were prepared by mixing in a Hobart mixer. The plastisolswere prepared with 100 parts PVC (Solvin 382 NG), 60 parts of the esterprepared according to examples 14, 20 and 29, respectively, and 1 partof a conventional stabilizer. The gelation temperatures of theplastisols were determined by an Anton Paar Physica Rheometer MCR 301.The instrument was used in oscillation mode, frequency 1 hz, amplitude0.01% and the heating rate was 10° C./min Dynamic mechanical analysis ofplastisols is shown in FIG. 2. The evolution of the Elastic modulus G′is plotted for each alcohol ester, in the range of temperature between80° C. and 140° C. The comparative example was based on DINP (availablefrom ExxonMobil). Note that in FIG. 2, elastic modulus is plotted as afunction of the heating temperature (heating rate is 10° C./min) The farleft line is the plasticizer derived from example 14, the second to thefar left line is DINP, the third to the far left line is the plasticizerderived from example 20, and the right line is the plasticizer derivedfrom example 29.

The 3′methyl-4-biphenyl carboxylic acid ester of C₉ alcohol (example 14)shows faster gelling (means G′ sudden increase occurs at a lower T°)than DINP while the 2,2′-biphenyl carboxylic acid ester of C₉ alcohols(example 20) and the 4,4′-biphenyl carboxylic acid ester of C₉ alcohols(example 28) are slower.

Example 30

The following example demonstrates a sample that was prepared by usingtoluene hydroalkylation/dehydrogenation, then oxidation to make amonoacid, which was esterified with a C₁₀ OXO-alcohol.

Example 30A Synthesis of 0.3% Pd/MCM-49 Catalyst for TolueneHydroalkylation

80 parts MCM-49 zeolite crystals were combined with 20 partspseudoboehmite alumina, on a calcined dry weight basis. The MCM-49 andpseudoboehmite alumina dry powder were placed in a Muller mixer andmixed for about 10 to 30 minutes. Sufficient water and 0.05% polyvinylalcohol was added to the MCM-49 and alumina during the mixing process toproduce an extrudable paste. The extrudable paste was formed into a 1/20inch (0.13 cm) quadrulobe extrudate using an extruder and the resultingextrudate was dried at a temperature ranging from 250° F. to 325° F.(120° C. to 163° C.). After drying, the extrudate was heated to 1000° F.(538° C.) under flowing nitrogen. The extrudate was then cooled toambient temperature and humidified with saturated air or steam. Afterthe humidification, the extrudate was ion exchanged with 0.5 to 1 Nammonium nitrate solution two times. The ammonium nitrate exchangedextrudate was then washed with deionized water to remove residualnitrate prior to calcination in air. The exchanged and dried extrudatewas then calcined in a nitrogen/air mixture to a temperature 1000° F.(538° C.). Afterwards, the calcined extrudate was cooled to roomtemperature. The 80% MCM-49, 20% Al₂O₃ extrudate was incipient wetnessimpregnated with a palladium (II) chloride solution (target: 0.30% Pd)and then dried overnight at 121° C. The dried catalyst was calcined inair at the following conditions: 5 volumes air per volume catalyst perminute, ramp from ambient to 538° C. at 1° C./min and hold for 3 hours.

Example 30B Toluene Hydroalkylation

The catalyst described above in example 30A was employed tohydroalkylate toluene in a fixed bed reactor as described below. Thereactor comprised a stainless steel tube having an outside diameter of:⅜ inch (0.95 cm), a length of 20.5 inch (52 cm) and a wall thickness of0.35 inch (0.9 cm). A piece of stainless steel tubing having a length of8¾ inch (22 cm) and an outside diameter of: ⅜ inch (0.95 cm) and asimilar length of ¼ inch (0.6 cm) tubing of were used in the bottom ofthe reactor (one inside of the other) as a spacer to position andsupport the catalyst in the isothermal zone of the furnace. A ¼ inch(0.6 cm) plug of glass wool was placed on top of the spacer to keep thecatalyst in place. A ⅛ inch (0.3 cm) stainless steel thermo-well wasplaced in the catalyst bed to monitor temperature throughout thecatalyst bed using a movable thermocouple.

The catalyst was sized to 20/40 sieve mesh or cut to 1:1 length todiameter ratio, dispersed with quartz chips (20/40 mesh) then loadedinto the reactor from the top to a volume of 5.5 cc. The catalyst bedwas approx. 15 cm in length. The remaining void space at the top of thereactor was filled with quartz chips, with a ¼ plug of glass wool placedon top of the catalyst bed being used to separate quartz chips from thecatalyst. The reactor was installed in a furnace with the catalyst bedin the middle of the furnace at a pre-marked isothermal zone. Thereactor was then pressure and leak tested (at approx. 300 psig (2170kPa)).

The catalyst was pre-conditioned in situ by heating to 25° C. to 240° C.with H₂ flow at 100 cc/min and holding for 12 hours. A 500 cc ISCOsyringe pump was used to introduce a chemical grade toluene feed to thereactor. The feed was pumped through a vaporizer before flowing throughheated lines to the reactor. A Brooks mass flow controller was used toset the hydrogen flow rate. A Grove “Mity Mite” back pressure controllerwas used to control the reactor pressure at approx. 150 psig (1135 kPa).GC analyses were taken to verify feed composition. The feed was thenpumped through the catalyst bed held at the reaction temperature of 120°C. to 180° C. at a WHSV of 2, hydrogen:hydrocarbon mole ratio of 2:1 anda pressure of 15-200 psig (204-1480 kPa). The liquid products exitingthe reactor flowed through heated lines were routed to two collectionpots in series, the first pot being heated to 60° C. and the second potcooled with chilled coolant to about 10° C. Material balances were takenat 12 to 24 hour intervals. Samples were taken and diluted with 50%ethanol for analysis. An Agilent 7890 gas chromatograph with FIDdetector was used for the analysis. The non-condensable gas productswere routed to an on line HP 5890 GC.

The product analysis done on the Agilent 7890 GC was performed with 150vial sample tray using the following procedure/conditions: 1) Inlet Tempof 220° C.; 2) Detector Temp of 240° C. (Col+make up=constant); 3) TempProgram of initial temp 120° C. hold for 15 min., ramp at 2° C./min to180° C., hold 15 min; ramp at 3° C./min to 220° C. and hold till end; 4)Column Flow of 2.25 ml/min (27 cm/sec); 5) Split mode, Split ratio100:1; 6) injector: Auto sampler (0.2 μl); 7). Column Parameters were:Two columns joined to make 120 Meters (coupled with Agilent ultimateunion, deactivated; Column # Front end—Supelco β-Dex 120: 60 m×0.25mm×0.25 μm film joined to Column #2 back end: γ—Dex 325: 60 m×0.25mm×0.25 μm film.

Example 30C Synthesis of 1% Pt/0.15% Sn/SiO₂ Catalysts forDehydrogenation

The catalyst was prepared by incipient wetness impregnation. In eachcase, a 1/20″ quadralobe silica extrudate was initially impregnated withan aqueous solution of tin chloride and then dried in air at 121° C. Theresultant tin-containing extrudates were then impregnated with anaqueous solution of tetraammine Pt nitrate and again dried in air at121° C. Each of the resultant products was calcined in air at 350° C.for 3 hours before being used in subsequent catalyst testing.

Example 30D Dehydrogenation

The hydroalkylation product described above (feed composition: 9%methylcyclohexane, 66% Toluene, 24% methylcyclohexyl toluene, 0.5%dialkylate) was fed to a dehydrogenation unit containing the 1% Pt/0.15%Sn/RT-235 catalyst prepared above in example 30C. The reactor used inthese experiments consists of a stainless steel tube. The StandardReactor is piping with dimensions: ⅜ in×20.5 in×0.35 in wall thickness.A piece of stainless steel tubing 8¾ in. long×⅜ in. o.d. and a piece of¼ inch tubing of similar length was used in the bottom of the reactor asa spacer (one inside of the other) to position and support the catalystin the isothermal zone of the furnace. A ¼ inch plug of glass wool wasplaced at the top of the spacer to keep the catalyst in place. A ⅛ inchstainless steel thermo-well was placed in the cat bed, long enough tomonitor temperature throughout the catalyst bed using a movablethermocouple. The catalyst is loaded with a spacer at the bottom to keepthe catalyst bed in the center of the furnace's isothermal zone.Typically, 1.0 g of catalyst was sized to 20/40 sieve mesh or cut to 1:1l/d and dispersed with quartz chips (20/40 mesh) to a volume of 5.5 cc.When loaded, the catalyst bed measured about 12.5 cm in height. Thereactor was topped off with the same size quartz or larger size up to 14mesh. The reactor was installed in a furnace with the catalyst bed inthe middle of the furnace at a pre-marked isothermal zone. The reactorwas then pressure and leak tested at approx. 300 psig.

The catalyst was pre-conditioned in situ; heated to 375° C. to 460° C.with H₂ flow at 100 cc/min and held for 2 hours. A 500 cc ISCO syringepump was used to introduce the hydroalkylated feed described above tothe reactor. The feed was pumped through a vaporizer before flowingthrough heated lines to the reactor. A Brooks mass flow controller wasused to set the hydrogen flow rate. A Grove “Mity Mite” back pressurecontroller was used to control the reactor pressure typically at 100psig. GC analyses were taken to verify feed composition. The feed wasthen pumped through the catalyst bed held at a reaction temperature of375° C. to 460° C. at a WHSV of 2 and a pressure of 100 psig. Theproducts exiting the reactor flowed through heated lines routed to twocollection pots in series. The non-condensable gas products were routedto an on line HP 5890 GC. The first pot was heated to 60° C. and thesecond pot cooled with chilled coolant to about 10° C. Material balanceswere taken at 12 and 24 hour intervals. Samples were taken and dilutedwith 50% ethanol for analysis. This product was distilled (see example30E below) to remove the unreacted toluene and the methylcyclohexanethat was produced.

Example 30E Distillation

Toluene and methyl cyclohexane were removed from the product of example30E using a rotovap setup at 70° C. under vacuum. For dimethyl biphenyldistillation the following setup was used: The crude dimethylbiphenylproduct was charged into a 3-necked-5-liter round bottom distillationflask attached to a 3′ oldershaw column (21 theoretical trays). Theround bottom was fitted with a thermometer, nitrogen sparger, chilledwater condenser and the column fed a multiple receiving adapter with anda dry ice/isopropanol cooled trap. The round bottom flask was heated at200° C. with a reflux ratio of 10:1. Approximately 50 gram distillationcuts were collected and analyzed by GC. The fractions which werecollected at 120-130° C. at a vacuum of 0.5-1 mmHg were combined afterthey were analyzed by GC. The combined sample was the re-analyzed by GC.The composition of this sample was: 2,3′DMBP-0.70%; 2,4′DMBP-2.54%;3,3′DMBP-19.74%; 3,4′DMBP-52.78%; 4,4′DMBP-24.23%. This sample was thenoxidized according to the procedure in example 30F below.

Example 30F Oxidation

Oxidation of the purified dehydrogenated feed produced in example 30E isdescribed below: Oxidation was done batchwise and the batches combinedbefore carrying out the monoacid isolation and purification. A 300 mlParr reactor was charged with 115.6 grams of feed, 1.45 grams of cobalt(II) chloride hexahydrate, 1.41 grams of didodecyl dimethylammoniumbromide and 1.25 grams of t-butylhydroperoxide. The reactor was sealedand pressurized to 500 psi with air. The air flow rate was set at 750cc/min. The reactor was heated to 150° C. with a stir rate of 1200 rpm.After 6 hours reaction time the reactor was cooled to room temperature,then depressurized. The reactor was disassembled and the contentsremoved.

Example 30G Mono-Acid Isolation

Five oxidation runs (722.1 grams) were combined and dissolved into 2500ml of methanol. The mixture was stirred and heated to reflux for onehour. The mixture was cooled to room temperature and the solids wereallowed to settle overnight. The above mixture was filtered to removemost of the di-acid. The methanol soluble portion was placed on aRotovap to remove the methanol. The residue was added to 2000 ml ofwater and cooled using an ice water bath. 200 grams of a 50% NaOHsolution was diluted with 200 ml of water. The NaOH solution was slowlyadded to the cooled water mixture maintaining the temperature below 20°C. The mixture was transferred to a separatory funnel and extracted withtoluene. The toluene was separated from the aqueous phase. The aqueousphase was cooled using an ice water bath. 100 ml of concentrated HCl,diluted with 100 ml water, was slowly added to precipitate themono-acid. The above mixture was filtered and the solids were washedthree times with water. The solids were then placed in a vacuum oven at60° C. under house vacuum to dry. 375 grams were recovered.

Example 30H Esterification of Monoacid

To a 2 liter round bottom flask fitted with a thermometer, Dean-Starktrap, condenser, air stirring and heating mantle was added 254.2 grams(1.2 moles) of the isolated monoacid described above, 570.76 grams (3.6moles) Exxal™ C10 alcohol and 100 ml xylenes. The mixture was slowlyheated and water was collected in the Dean-Stark trap. The finaltemperature attained after 23 hrs was 194° C. and the total watercollected was 87.4 grams. The mixture was cooled to room temperature.The mixture was transferred to a distillation flask where the xylenesand unreacted alcohol were removed. The maximum temperature was 212° C.at 0.2 mmHg 417.0 grams of residue remained for distillation.

Example 30I Purification (Distillation) of Monoester

The esterified mixture from example 3H was placed in a Kugelrohr and themonoester was distilled at greater than 200° C. at 0.05 mmHg. Thedistilled monoester was further purified by column chromatography.

General Procedure for Column Chromatography: Preparation of Columns:

Silica gel (70-90 um, 60A) is dispensed from a 25 kilogram drum using alarge plastic scoop. The silica is transferred from the drum to a large(4 L) beaker located inside the fume hood. The silica is then slurriedin several liters of hexanes, using manual stirring. Once flow isestablished, the silica slurry is poured into a 3000 mL, 150M fritted,glass funnel, which sits atop a 4 L vacuum flask. Once the silica hassettled, vacuum is applied on the flask, allowing the silica gel topack. The resulting silica bed is 5.5 inches wide and approximately 6inches in height. Resulting fractions were analyzed by Thin LayerChromatography (TLC) in 5% ethyl acetate in hexanes.

After the distillation in example 301 above, samples were run in batchesof 100-200 g each. With the flask is under vacuum, 100 g of impureester, dissolved in minimum amount of hexanes, is added to the packedsilica gel. Product is then eluted by washing the silica bed with 3.8liters of 5% ethyl acetate in hexanes (Fraction 1), followed by 1 literof 5% ethyl acetate in hexanes (Fraction 2).

Analysis of fractions by TLC indicates purified ester with a faint traceof impurity.

Fractions were combined and concentrated down on a rotary evaporator,under vacuum, at 50° C. before final drying overnight under pump vacuum.Yield, after vacuum drying, is ˜85% of mostly colorless, but slightlycloudy, viscous liquid.

After column purification the mixture was front end stripped using theKugelrohr. The stripped monoester was bubbled with nitrogen to removecloudiness. GC analysis of the final product was consistent withformation of a mixture of OXO-C₁₀ monoester isomers (99%).

This invention also relates to:

1. Compounds of the formula

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a hydrocarbonresidue of a C₄ to C₁₄ OXO-alcohol.2. The compounds of clause 1, wherein R₁ is located at the ortho-, meta-or para-position.3. The compounds of clause 1, wherein R₁ is phenyl located at thepara-position.4. The compounds of clause 1, wherein R₁ is an alkyl and/or anOXO-ester-substituted phenyl at the ortho-, meta-, or para-position.5. The compounds of clause 1, wherein R₁ is an alkyl and/or anOXO-ester-substituted cyclohexyl at the ortho-, meta-, or para-position.6. The compounds of any of the preceding clauses, wherein R₂ is thehydrocarbon residue of a C₅ to C₁₀ OXO-alcohol averaging from 0.2 to 5.0branches per residue.7. The compounds of any of the preceding clauses, wherein thehydrocarbon residue averages from 0.05 to 0.4 branches per residue atthe alcoholic beta carbon.8. The compounds of any of the preceding clauses, wherein thehydrocarbon residue averages at least 1.3 to 5.0 methyl branches perresidue.9. The compounds of any of the preceding clauses, wherein thehydrocarbon residue averages from 0.35 to 1.5 pendant methyl branchesper residue.10. A process for making compounds of the formula:

wherein R₁ is a cyclic hydrocarbon optionally substituted with an alkyland/or an OXO-ester, and R₂ is a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol, comprising the steps of: reacting benzene or alkylatedbenzene under conditions appropriate to form alkylated biphenyl;optionally alkylating biphenyl to form said alkylated biphenyl;oxidizing the alkyl group(s) on said alkylated biphenyl to form at leastone acid group; and reacting said acid group(s) with an OXO-alcoholunder esterification conditions to form said compounds.11. The process of clause 10, wherein said reacting step is conductedwith benzene, and said optional alkylating step is conducted with analcohol.12. The process of clauses 10-11, wherein said alcohol is methanol andsaid alkylating step is conducted in the presence of an acid catalyst.13. The process of clause 10, wherein said reacting step is conductedwith benzene, further comprising the steps of: hydroalkylating benzeneby reacting benzene in the presence of H₂ to hydrogenate one mole ofsaid benzene to form cyclohexene, alkylating benzene with saidcyclohexene to form cyclohexylbenzene; dehydrogenating saidcyclohexylbenzene to form biphenyl; and alkylating one or both aromaticmoieties of said biphenyl to form said alkylated biphenyl.14. The process of clause 13, wherein said hydroalkylating step isconducted in the presence of a hydrogenation catalyst, said alkylatingstep is conducted with an alkylation catalyst, and said dehydrogenatingstep is conducted with a dehydrogenation catalyst.15. The process of clause 14, wherein said hydrogenation catalyst isselected from the group consisting of platinum, palladium, ruthenium,nickel, zinc, tin, cobalt, or a combination of these metals, withpalladium being particularly advantageous; said alkylation catalyst isselected from the group consisting of Zeolite, mixed metal oxides andsaid dehydrogenation catalyst is selected from the group consisting ofplatinum, pladium, Ru, Rh, nickel, zinc, tin, cobalt and combinationsthereof.16. The process of clause 10, wherein said reacting step is conductedwith benzene in the presence of oxygen and an oxidative couplingcatalyst, forming biphenyl, further comprising the step of: alkylatingone or both aromatic moieties of said biphenyl to form said alkylatedbiphenyl.17. The process of clause 16, wherein said alkylating step is conductedwith an alkylation catalyst.18. The process of clause 10, wherein the reacting step is conductedwith toluene, further comprising the steps of: reacting toluene in thepresence of H₂ and a hydrogenation catalyst to form methyl cyclohexene;reacting said methyl cyclohexene with toluene in the presence of analkylation catalyst to form methyl cyclohexyl toluene; anddehydrogenating said methyl cyclohexyl toluene in the presence of adehydrogenation catalyst to form the alkylated biphenyl, which isdimethyl-biphenyl.19. A polymer composition comprising a thermoplastic polymer and atleast one plasticizer of the formula:

wherein R₁ is a saturated and unsaturated cyclic hydrocarbon optionallysubstituted with an alkyl and/or an OXO-ester, and R₂ is a hydrocarbonresidue of a C₄ to C₁₄ OXO-alcohol.20. A polymer composition comprising a thermoplastic polymer and atleast one compound of any of claims 1 to 9 or the product of the processof any of claims 10 to 18.21. The polymer composition of clause 19 or 20, wherein thethermoplastic polymer is selected from the group consisting of vinylchloride resins, polyesters, polyurethanes, ethylene-vinyl acetatecopolymer, rubbers, poly(meth)acrylics and combinations thereof.22. The composition of clause 1 wherein R¹ is tolyl and R¹ is a C₉ orC₁₀ hydrocarbyl.23. The composition of clauses 1 to 9, or 22 wherein the compoundcomprises analogs that have been fully or partially hydrogenated.24. The composition of clause 1 or 23 wherein R¹ is a saturated orunsaturated cyclic hydrocarbon substituted with an OXO-ester.25. The polymer composition of clause 19, 20 or 21 wherein thethermoplastic polymer is polyvinyl chloride.26. A mixture comprising at least two compounds of the formula:

wherein in the first compound, R₁ is a saturated cyclic hydrocarbonoptionally substituted with an alkyl and/or an OXO-ester, and R₂ is a C₄to C₁₄ hydrocarbyl, preferably a hydrocarbon residue of a C₄ to C₁₄OXO-alcohol; and in the second compound R₁ is an unsaturated cyclichydrocarbon optionally substituted with an alkyl and/or an OXO-ester,and R₂ is a C₄ to C₁₄ hydrocarbyl, preferably a hydrocarbon residue of aC₄ to C₁₄ OXO-alcohol.27. The mixture of clause 26 where each R¹ is a C₆ ring optionallysubstituted with an alkyl and/or an OXO-ester.28. A mixture comprising at least two compounds of the formula:

wherein each R₁ is, independently, a saturated or unsaturated cyclichydrocarbon optionally substituted with an alkyl and/or an OXO-ester,and each R₂ is, independently, a C₄ to C₁₄ hydrocarbyl, preferably ahydrocarbon residue of a C₄ to C₁₄ OXO-alcohol.29. A wire and cable coating formulation comprising: i) 100 parts byweight PVC; (ii) 20 to 80 parts of the compounds of any of clauses 1-9,22, 24, 26, 27 or 28; (iii) a filler; and (iv) a stabilizer.30. A cable insulation formulation according to clause 29 wherein thefiller is present at from 1 to 100 parts by weight per 100 parts of thePVC and the stabilizer is present at from 5 to 15 parts by weight per100 parts of the PVC.31. A cable filling compound formulation according to clause 29 whereinthe filler is present at from 1 to 600 parts by weight per 100 parts ofthe PVC and the stabilizer is present at from 5 to 15 parts by weightper 100 parts of the PVC.32. A wire or cable coated with a composition or formulation of clause19-21, 25, 29 or 30.33. A composition according to clause 19-21, wherein the compositioncomprises the plasticizer of claim 1 in an amount of from 5 to 90% bymass per 100 parts by mass of the polymer.34. A composition according to clause 19-21 wherein the compositioncomprises additional plasticizer selected from the group consisting of adialkyl phthalate, a trialkyl trimellite, a dialkyl adipate, a dialkylterephthalate, a dialkyl cyclohexanedicarboxylate, a benzoic ester, aglycol ester, an alkylsulphonic ester, a glycerol ester, an isosorbideester, a citric ester, an alkylpyrrolidone, and an epoxidized oil.35. A composition according to clause 19-21, further comprising: a PVCsuspension, a PVC microsuspension, a PVC emulsion, or a combinationthereof.36. A composition according to clause 19-21, further comprising: anadditive selected from the group consisting of a filler, a pigment, amatting agent, a heat stabilizer, an antioxidant, a UV stabilizer, aflame retardant, a viscosity regulator, a solvent, a deaerating agent,an adhesion promoter, a process aid, and a lubricant.37. A floor covering, comprising: the composition according to clause35.38. A wallpaper, comprising: the composition according to clause 35.39. A tarpaulin, comprising the composition according to clause 35.40. A coated textile, comprising: the composition according to clause35.41. A wall covering, comprising: the composition according to clause 35.42. A film, comprising: the composition according to clause 35 whereinthe film is a roofing sheet, a tarpaulin, an advertising banner,synthetic leather, packaging film, a medical article, a toy, a seal, oran automobile interior article.

The meanings of terms used herein shall take their ordinary meaning inthe art; reference shall be taken, in particular, to Handbook ofPetroleum Refining Processes, Third Edition, Robert A. Meyers, Editor,McGraw-Hill (2004). In addition, all patents and patent applications(including priority documents), test procedures (such as ASTM methods),and other documents cited herein are fully incorporated by reference tothe extent such disclosure is not inconsistent with this disclosure andfor all jurisdictions in which such incorporation is permitted. Also,when numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.Note further that Trade Names used herein are indicated by a™ symbol,indicating that the names may be protected by certain trademark rights,e.g., they may be registered trademarks in various jurisdictions.

The disclosure has been described above with reference to numerousembodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

1. A compound represented by the formula:

wherein R₁ is a saturated or unsaturated cyclic hydrocarbon substitutedwith an OXO-ester, and R₂ is a C₄ to C₁₄ hydrocarbyl.
 2. The compound ofclaim 1, wherein R₁ is located at the ortho-, meta- or para-position. 3.(canceled)
 4. The compound of claim 2, wherein R₁ is a phenyl grouplocated at the para-position where the phenyl is substituted with anOXO-ester at the ortho-, meta-, or para-position.
 5. (canceled)
 6. Thecompound of claim 1, wherein R₂ is not linear.
 7. The compound of claim1, wherein R₂ is branched. 8.-12. (canceled)
 13. The compound of claim 1wherein R¹ is a saturated or unsaturated cyclic hydrocarbon substitutedwith an OXO-ester.
 14. A mixture comprising at least two compounds ofclaim
 1. 15. The mixture of claim 14, wherein in the first compound, R₁is a saturated cyclic hydrocarbon substituted with OXO-ester, and in thesecond compound R₁ is an unsaturated cyclic hydrocarbon substituted withan OXO-ester.
 16. The mixture of claim 15 where each R¹ is a C₆ ringoptionally substituted with an OXO-ester.
 17. A process for makingcompounds of the formula:

wherein R₁ is a cyclic hydrocarbon substituted with an OXO-ester, and R₂is a C₄ to C₁₄ alkyl group, comprising the steps of: reacting benzene oralkylated benzene under conditions appropriate to form alkylatedbiphenyl; optionally alkylating biphenyl to form said alkylatedbiphenyl; oxidizing the alkyl group(s) on said alkylated biphenyl toform acid groups; and reacting said acid groups with an OXO-alcoholunder esterification conditions to form said compounds, wherein afterreacting said acid groups with an OXO-alcohol under esterificationconditions, the reaction product is contacted with a basic solution.18.-38. (canceled)
 39. A mixture of compounds represented by theformulas:

and one or more of

wherein each R₃ is, independently, —Co₂R₂*, R₂ is a C₄ to C₁₄hydrocarbyl, R₂* is a C₄ to C₁₄ hydrocarbyl, that may be the same ordifferent as R₂.
 40. The mixture of claim 39, wherein each R₂ is,independently, a C₆ to C₉ hydrocarbyl.
 41. The mixture of claim 39,wherein each R₂ is, independently, a C₆, C₇, C₈ or C₉ alkyl.
 42. Themixture of claim 39, wherein each R₂ is, independently, hexyl, heptyl,octyl or nonyl, or an isomer thereof.
 43. The mixture of claim 39,wherein the mixture comprises:

where each R₂ is, independently, a C₄ to C₁₄ hydrocarbyl.